WO2022107034A1 - Rubber modified bituminous binders - Google Patents
Rubber modified bituminous binders Download PDFInfo
- Publication number
- WO2022107034A1 WO2022107034A1 PCT/IB2021/060691 IB2021060691W WO2022107034A1 WO 2022107034 A1 WO2022107034 A1 WO 2022107034A1 IB 2021060691 W IB2021060691 W IB 2021060691W WO 2022107034 A1 WO2022107034 A1 WO 2022107034A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- rubber modified
- modified bituminous
- bituminous binder
- binder
- digested
- Prior art date
Links
- 239000011230 binding agent Substances 0.000 title claims abstract description 303
- 229920001971 elastomer Polymers 0.000 title claims abstract description 192
- 239000005060 rubber Substances 0.000 title claims abstract description 192
- 239000010426 asphalt Substances 0.000 claims abstract description 107
- 238000000034 method Methods 0.000 claims abstract description 59
- 230000001939 inductive effect Effects 0.000 claims abstract description 41
- 239000006259 organic additive Substances 0.000 claims abstract description 25
- 238000003860 storage Methods 0.000 claims abstract description 10
- 238000007789 sealing Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims description 166
- 229920002209 Crumb rubber Polymers 0.000 claims description 109
- 238000012360 testing method Methods 0.000 claims description 55
- 238000013461 design Methods 0.000 claims description 27
- 238000011084 recovery Methods 0.000 claims description 21
- 229920013729 reactive elastomeric terpolymer Polymers 0.000 claims description 18
- 238000010998 test method Methods 0.000 claims description 17
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 16
- 238000007906 compression Methods 0.000 claims description 14
- 230000006835 compression Effects 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- 229920001897 terpolymer Polymers 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 10
- 239000005977 Ethylene Substances 0.000 claims description 10
- 125000000524 functional group Chemical group 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 4
- 238000006073 displacement reaction Methods 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 230000035882 stress Effects 0.000 description 45
- 230000029087 digestion Effects 0.000 description 32
- 239000000654 additive Substances 0.000 description 24
- 230000000996 additive effect Effects 0.000 description 18
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 17
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 17
- 238000002156 mixing Methods 0.000 description 12
- 238000009472 formulation Methods 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 230000035515 penetration Effects 0.000 description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 230000035508 accumulation Effects 0.000 description 6
- 238000009825 accumulation Methods 0.000 description 6
- 238000011010 flushing procedure Methods 0.000 description 6
- 238000011835 investigation Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 238000010276 construction Methods 0.000 description 5
- 239000004606 Fillers/Extenders Substances 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 238000005056 compaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 206010049119 Emotional distress Diseases 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000009429 distress Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- 239000011387 rubberized asphalt concrete Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 238000013401 experimental design Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000004154 testing of material Methods 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 241000519995 Stachys sylvatica Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000011384 asphalt concrete Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2495/00—Bituminous materials, e.g. asphalt, tar or pitch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2555/00—Characteristics of bituminous mixtures
- C08L2555/20—Mixtures of bitumen and aggregate defined by their production temperatures, e.g. production of asphalt for road or pavement applications
- C08L2555/22—Asphalt produced above 140°C, e.g. hot melt asphalt
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2555/00—Characteristics of bituminous mixtures
- C08L2555/30—Environmental or health characteristics, e.g. energy consumption, recycling or safety issues
- C08L2555/34—Recycled or waste materials, e.g. reclaimed bitumen, asphalt, roads or pathways, recycled roof coverings or shingles, recycled aggregate, recycled tires, crumb rubber, glass or cullet, fly or fuel ash, or slag
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2555/00—Characteristics of bituminous mixtures
- C08L2555/40—Mixtures based upon bitumen or asphalt containing functional additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2555/00—Characteristics of bituminous mixtures
- C08L2555/40—Mixtures based upon bitumen or asphalt containing functional additives
- C08L2555/80—Macromolecular constituents
Definitions
- This Invention relates to rubber modified bituminous binders.
- the invention relates to a method of re-stiffening an over-digested rubber modified bituminous binder, to a rubber modified bituminous binder, and to a method of sealing or asphalt paving a surface.
- the typical base bitumen or base bituminous binder conventionally used in South Africa was the 70/100 penetration grade bitumen conforming to the requirements of South African National Standard 4001-BT1 [SANS 4001-BT1], 2014. Penetration Grade Bitumens (Edition 1.2).
- the extender oil was produced as per the requirements of the Committee of Land Transport Officials ([COLTO] (1998), Standard Specifications for Road and Bridge Works for State Road authorities (1998 Edition), South Africa: South African Institution of Civil Engineering) (hereinafter referred to as COLTO, 1998). Rubber crumbs of the grading requirements stated in TGI, 2015 are recommended.
- the rubber crumb particles essentially pass a 1.00 mm sieve (1.18 mm was the requirement in a previous guideline document i.e., TGI, 2007) and the majority is retained on a 0.6 mm sieve.
- the crumb rubber is thus digested in bitumen using a combination of high temperatures, agitation and controlled digestion times.
- the limitations of this production route have historically been the high handling temperatures, the heterogeneous nature of rubber modified bituminous binder material and the limited window period of application for these binder materials to have optimum performance.
- a method of restiffening an over-digested rubber modified bituminous binder including admixing a reactive, stiffness inducing organic additive with the over-digested rubber modified bituminous binder to produce a re-stiffened rubber modified bituminous binder with an increased softening point, wherein the admixing takes place at an elevated temperature of at least 185°C.
- the re-stiffened rubber modified bituminous binder also exhibits an improved J nr .
- An improved J nr is a J nr value, in kPa -1 , for the re-stiffened rubber modified bituminous binder, which is lower than said J nr value, in kPa -1 , for the over-digested rubber modified bituminous binder, over a stress range of at least 100- 10000 Pa, using a multiple stress creep and recovery test.
- the re-stiffened rubber modified bituminous binder typically also exhibits an improved storage stability.
- An improved storage stability is a storage stability value, in °C, for the re-stiffened rubber modified bituminous binder, which is lower than said storage stability value, in °C, for the over-digested rubber modified bituminous binder using a storage stability of polymer modified binders (TGI MB-6) test.
- the re-stiffened rubber modified bituminous binder typically also exhibits an improved stress resilience.
- An improved stress resilience is J nr values, in kPa -1 , for the re-stiffened rubber modified bituminous binder, which display a lower change with increased stress than said J nr values, in kPa -1 , for the over-digested rubber modified bituminous binder, over a stress range of at least 100 - 10000 Pa, using a multiple stress creep and recovery test.
- an over-digested rubber modified bituminous binder is a rubber modified bituminous binder with a viscosity at 190°C of less than 2000 mPa.s and/or with a softening point of less than 55°C.
- the over-digested rubber modified bituminous binder is completely over-digested.
- a completely over-digested rubber modified bituminous binder is an overdigested rubber modified bituminous binder whose viscosity approaches that of a base bituminous binder of the rubber modified bituminous binder, once the viscosity has dropped below 2000 mPa.s, and/or a completely over-digested rubber modified bituminous binder is an over-digested rubber modified bituminous binder whose softening point approaches that of the base binder, once the softening point has dropped below 55°C.
- the method of the invention may include digesting the over-digested rubber modified bituminous binder for a period of time sufficient to ensure that the overdigested rubber modified bituminous binder is completely over-digested, prior to admixing the reactive, stiffness inducing organic additive with the over-digested rubber modified bituminous binder.
- the rubber in the rubber modified bituminous binder may be crumb rubber.
- the crumb rubber may be as hereinbefore described, e.g. in accordance with TG 1, 2015.
- the bitumen in the rubber modified bituminous binder may include a base bitumen as hereinbefore described and the rubber modified bituminous binder, prior to becoming over-digested, may be prepared in accordance with the guidelines set out in TG 1, 2015.
- the rubber modified bituminous binder may thus include an extender oil or high boiling point fluxing agents.
- the reactive, stiffness inducing organic additive may be reactive in the sense that reactions between one or more components of the reactive, stiffness inducing organic additive react(s) with functional groups present in the over-digested rubber modified bituminous binder to produce a re-stiffened rubber modified bituminous binder with an altered composition and an increased softening point.
- these reactions provide an increase (compared to over-digested rubber modified bituminous binder) in weight fraction of components of the re-stiffened rubber modified bituminous binder with a molar mass over at least part of a molar mass range between 2xl0 6 and 8xl0 6 g/mol, or between 2xl0 6 and 7xl0 6 g/mol, or between 3xl0 6 and 8xl0 6 g/mol or between 3X10 6 and 7xl0 6 g/mol, e.g. between 4xl0 6 and 6xl0 6 g/mol.
- the reactive, stiffness inducing organic additive may be reactive in the sense that reactions between one or more components of the reactive, stiffness inducing organic additive react(s) with functional groups (e.g. carboxylic acid functional groups) present in the overdigested rubber modified bituminous binder to produce a re-stiffened rubber modified bituminous binder with an improved J nr , and/or an improved storage stability and/or an improved stress resilience.
- functional groups e.g. carboxylic acid functional groups
- the reactive, stiffness inducing organic additive may be a reactive elastomeric organic additive.
- the reactive, stiffness inducing organic additive may be a reactive elastomeric polymer composition.
- the reactive, stiffness inducing organic additive may be a reactive elastomeric terpolymer composition.
- the terpolymer composition may include ethylene as a monomer. Instead, or in addition, the terpolymer may include an alkyl acrylate as a monomer. Instead, or in addition, the terpolymer may include glycidyl methacrylate as a monomer.
- the reactive elastomeric terpolymer is a terpolymer of ethylene, an alkyl acrylate and glycidyl methacrylate.
- An example of such a terpolymer is a reactive stiffness inducing terpolymer of ethylene/n-butyl acrylate/glycidyl methacrylate.
- the glycidyl methacrylate may be present in a concentration of about 9% by mass.
- the admixing of the reactive, stiffness inducing organic additive with the overdigested rubber modified binder should be in the absence of poly-phosphoric acid.
- poly-phosphoric acid which is often used with products such as a terpolymer composition of ethylene/n-butyl acrylate/glycidyl methacrylate
- the admixing takes place at an elevated temperature of between about 185°C and about 210°C, more preferably between about 190°C and about 200°C, most preferably between about 190°C and about 195°C, e.g. at about 193°C.
- the admixing may be for less than about 160 minutes, preferably less than about 145 minutes, more preferably less than about 130 minutes, e.g. about 120 minutes.
- the admixing may be for at least about 100 minutes, preferably at least about 110 minutes, more preferably at least about 120 minutes.
- the re-stiffened rubber modified bituminous binder may have an increased softening point to at least 56°C, preferably to at least 58°C, more preferably to at least 60°C, e.g. to at least 61°C.
- the re-stiffened rubber modified bituminous binder may show a reduction in elasticity with an increase in the complex modulus (G*), as evidenced by reduced phase angles at high in-service temperatures. This can best be seen on a Black diagram plot of complex modulus versus phase angle, at various frequencies and in-service temperatures, using data from a dynamic shear rheometer.
- high in-service temperatures is meant a temperature at which the restiffened rubber modified bituminous binder would normally be used to resist deformation, e.g. when an asphalt road carries traffic in a hot summer season, i.e. at temperatures in the range of between about 20°C and about 70°C.
- the stiffness inducing organic additive and the over-digested rubber modified binder may be admixed in a mass ratio of between about 0.5:99.5 and about 2.0:98.0, preferably between about 0.5:99.5 and about 1.5:98.5, more preferably between about 0.8:99.2 and about 1.2:98.8, e.g. about 1.0:99.0.
- the invention extends to a re-stiffened rubber modified bituminous binder when produced by the method of re-stiffening an over-digested rubber modified bituminous binder as hereinbefore described.
- the re-stiffened rubber modified bituminous binder may have a softening point of at least 56°C, preferably at least 58°C, more preferably at least 60°C, e.g. at least 61°C.
- the re-stiffened rubber modified bituminous binder has an increased weight fraction (compared to over-digested rubber modified bituminous binder) of components of the re-stiffened rubber modified bituminous binder with a molar mass over at least part of a molar mass range between 2xl0 6 and 8xl0 6 g/mol, or between 2xl0 6 and 7xl0 6 g/mol, or between 3xl0 6 and 8xl0 6 g/mol or between 3X10 6 and 7xl0 6 g/mol, e.g.
- the re-stiffened rubber modified bituminous binder produced by the method of re-stiffening an over-digested rubber modified bituminous binder may have a dynamic viscosity at 190°C of less than about 2000 mPa.s, or less than about 1500 mPa.s, or less than about 1200 mPa.s, or less than about 1000 mPa.s, or less than about 900 mPa.s, e.g. about 800 mPa.s.
- the dynamic viscosity of the re-stiffened rubber modified bituminous binder will depend on the formulation thereof, and on the reactive, stiffness inducing organic additive used.
- the re-stiffened rubber modified bituminous binder has a dynamic viscosity at 190°C of at least 100 mPa.s.
- a rubber modified bituminous binder including a digested rubber bituminous admixture with a softening point of at least 55°C and a dynamic viscosity at 190°C of less than 2000 mPa.s.
- the rubber modified bituminous binder has a softening point of at least 56°C, more preferably at least 58°C, most preferably at least 60°C, e.g. at least 61°C.
- the softening point will depend on the formulation of the rubber modified bituminous binder.
- the rubber modified bituminous binder may have a dynamic viscosity at 190°C of less than about 1500 mPa.s, or less than about 1200 mPa.s, or less than about 1000 mPa.s, or less than about 900 mPa.s, e.g. about 800 mPa.s.
- the dynamic viscosity will depend on the formulation of the rubber modified bituminous binder.
- the rubber modified bituminous binder has a dynamic viscosity at 190°C of at least 100 mPa.s.
- the rubber modified bituminous binder may have a compression recovery at 5 minutes, according to the MB-ll test method as set out in TG 1, 2015, of more than 70%, or more than 80%. As will be appreciated, the compression recovery at 5 minutes will depend on the formulation of the rubber modified bituminous binder.
- the rubber modified bituminous binder, or the re-stiffened rubber modified bituminous binder may have a compression recovery after 1 hour, according to the MB-ll test method, of more than 70%, preferably more than 75%, more preferably more than 80%, e.g. 85.6%.
- the compression recovery after 1 hour will depend on the formulation of the rubber modified bituminous binder
- the rubber modified bituminous binder, or the re-stiffened rubber modified bituminous binder may have a compression recovery after 24 hours, according to the MB-ll test method, of more than 40%, preferably more than 50%, more preferably more than 60, e.g. 69.9. As will be appreciated, the compression recovery after 24 hours will depend on the formulation of the rubber modified bituminous binder.
- the rubber modified bituminous binder, or the re-stiffened rubber modified bituminous binder may have a compression recovery after 4 days, according to the MB-ll test method, of more than 40, preferably more than 50%, more preferably more than 60%, e.g. 67.9%.
- the compression recovery after 4 days hours will depend on the formulation of the rubber modified bituminous binder.
- the rubber modified bituminous binder may have a resilience at 25°C, according to the MB-10 test method as set out in TG 1, 2015, of more than 13%, preferably more than 14%, more preferably more than 15%, e.g. 17.3%.
- the resilience at 25°C will depend on the formulation of the rubber modified bituminous binder.
- the rubber modified bituminous binder, or the re-stiffened rubber modified bituminous binder may flow, according to the MB-12 test method as set out in TG 1, 2015, more than 10mm, or more than 15mm, preferably more than 20mm, more preferably more than 25mm, e.g. 28mm. As will be appreciated, the flow will depend on the formulation of the rubber modified bituminous binder.
- the rubber modified bituminous binder or the re-stiffened rubber modified bituminous binder, has a weight fraction of at least about 0.13, preferably at least about 0.15, more preferably at least about 0.18, most preferably at least about 0.2 of components with an average molar mass between 3.9xl0 6 g/mol and 4.1xl0 6 g/mol.
- the rubber modified bituminous binder or the re-stiffened rubber modified bituminous binder, has a weight fraction of at least about 0.13, preferably at least about 0.15, more preferably at least about 0.18, most preferably at least about 0.2 of components with an average molar mass between 4.1xl0 6 g/mol and 4.2xl0 6 g/mol.
- said weight fraction will depend on the formulation of the rubber modified bituminous binder.
- the rubber modified bituminous binder may include reaction products from reactions between glycidyl methacrylate and functional groups of the over-digested bituminous binder (e.g. carboxylic acid groups).
- the rubber modified bituminous binder may be produced by a method of restiffening an over-digested rubber modified bituminous binder as hereinbefore described.
- the rubber modified bituminous binder may be produced from over-digested rubber modified bituminous binder.
- the over-digested rubber modified bituminous binder may be as hereinbefore described.
- the rubber in the rubber modified bituminous binder may be crumb rubber.
- the rubber modified bituminous binder, or the re-stiffened rubber modified bituminous binder, may be for use as a surface seal in a method of sealing a surface.
- the rubber modified bituminous binder, or the re-stiffened rubber modified bituminous binder may be for use as a binder in an asphalt mix for asphalt paving a surface.
- a method of sealing or asphalt paving a surface including applying a layer which includes a rubber modified bituminous binder to the surface, the rubber modified bituminous binder being in the form of a digested rubber bitumen admixture with a softening point of at least 55°C and a dynamic viscosity at 190°C of less than 2000 mPa.s.
- the layer typically includes aggregate particles, particularly when the method is an asphalt paving method.
- the rubber modified bituminous binder and the aggregate particles thus may a seal surfacing layer or a layer of an asphalt mix.
- the method of sealing or asphalt paving a surface may thus be a method of paving a surface with asphalt or an asphalt mix, sometimes referred to as asphalt concrete.
- the asphalt mix may be a medium continuously graded mix and may have a maximum displacement (using a Universal Testing Machine test setup, i.e. a UTM-25 test setup for dynamic modulus testing, with gyratory compacted specimens size of 100 mm diameter and 150mm high cored from cylindrical medium continuous specimens of 150 mm in diameter by 170 mm high, a single applied stress (deviator stress) level of 276 kPa and 69kPa confinement pressure at 40°C, with the deviator stress repeatedly pulsed in the vertical direction on the specimens using a haversine pulse load of 0.1 seconds and 0.9 seconds rest period until flow or 10,000 load cycles) equal to an identical asphalt SBS mix (in terms of mix design, grading, aggregate type and binder content) based on an A-E2 conforming SBS binder, preferably better than (e.g. at least 25% better), more preferably notably better than (e.g. at least 50% better), most preferably more than double, the performance, e.g. 1.6
- the asphalt mix may be a medium continuously graded mix and may have a flow number (using a UTM-25 test setup for dynamic modulus testing, with gyratory compacted specimens size of 100 mm diameter and 150mm high cored from cylindrical medium continuous specimens of 150 mm in diameter by 170 mm high, a single applied stress (deviator stress) level of 276 kPa and 69kPa confinement pressure at 40°C, with the deviator stress repeatedly pulsed in the vertical direction on the specimens using a haversine pulse load of 0.1 seconds and 0.9 seconds rest period until flow or 10,000 load cycles) equal to an identical asphalt SBS mix (in terms of mix design, grading, aggregate type and binder content) based on an A-E2 conforming SBS binder, preferably better than (e.g. at least 25% better), more preferably notably better than (e.g. at least 50% better), most preferably more than double, the performance, e.g. 5700-8700 as opposed to 900-2000, of the identical
- the asphalt mix may be a bitumen-rubber asphalt semi-open (BRASO) graded mix and may have a maximum displacement (using a UTM-25 test setup for dynamic modulus testing, with gyratory compacted specimens size of 100 mm diameter and 150mm high cored from cylindrical medium continuous specimens of 150 mm in diameter by 170 mm high, a single applied stress (deviator stress) level of 276 kPa and 69kPa confinement pressure at 40°C, with the deviator stress repeatedly pulsed in the vertical direction on the specimens using a haversine pulse load of 0.1 seconds and 0.9 seconds rest period until flow or 10,000 load cycles) equal to an identical asphalt mix (in terms of mix design, grading, aggregate type and binder content) based on an A-Rl conforming crumb rubber modified bituminous binder, preferably better than (e.g.
- BRASO bitumen-rubber asphalt semi-open
- the performance e.g. 0.7-1.1mm as opposed to 3.5-7.5mm, of the identical asphalt mix based on an A-Rl conforming crumb rubber modified bituminous binder.
- the asphalt mix may be a bitumen-rubber asphalt semi-open (BRASO) graded mix and may have a flow number (using a UTM-25 test setup for dynamic modulus testing, with gyratory compacted specimens size of 100 mm diameter and 150mm high cored from cylindrical medium continuous specimens of 150 mm in diameter by 170 mm high, a single applied stress (deviator stress) level of 276 kPa and 69kPa confinement pressure at 40°C, with the deviator stress repeatedly pulsed in the vertical direction on the specimens using a haversine pulse load of 0.1 seconds and 0.9 seconds rest period until flow or 10,000 load cycles) equal to an identical asphalt mix (in terms of mix design, grading, aggregate type and binder content) based on an A- R1 conforming crumb rubber modified bituminous binder, preferably better than (e.g.
- BRASO bitumen-rubber asphalt semi-open
- the performance e.g. 7400-8800 as opposed to 1400-4200, of the identical asphalt mix based on an A-Rl conforming crumb rubber modified bituminous binder.
- the rubber modified bituminous binder may be as hereinbefore described.
- the aggregate particles may be conventional aggregate particles e.g. used in paving, such as road construction, and the ratio of rubber modified bituminous binder and aggregate particles in the layer may be entirely conventional.
- FIGURE 1-1 shows a graph of the size grading of crumb rubber particles used in studies conducted by the inventor
- FIGURE 1-2 shows scanning electron microscope (SEM) photographs of the rubber crumbs, illustrating the surface texture/morphology of the rubber crumbs;
- FIGURE 2-1 shows a typical digestion viscosity curve of crumb rubber modified bituminous binder
- FIGURE 2-2 shows digestion viscosity curves of crumb rubber modified bituminous binders or blends at different handling temperatures, as a function of time;
- FIGURE 2-3 shows a Black diagram of crumb rubber modified bituminous binder (CRM binder) with PAV-ageing before and after solvent-soluble recovery;
- FIGURE 2-4 shows digestion viscosity curves of two crumb rubber modified bituminous binders or blends at 190-200°C, as a function of time;
- FIGURE 2-5 shows digestion viscosity curves of two crumb rubber modified bituminous binders or blends based on base binders from different refineries at 190-200°C as a function of time, with the solid bold horizontal lines representing the maximum and minimum TG 1 limits;
- FIGURE 2-6 shows a photographs of non-flushing (CRM bitumen 1) and flushing (CRM bitumen 2) areas;
- FIGURE 2-7 shows softening point curves with digestion time of crumb rubber modified bituminous blends or binders at 190-200°C, with the solid bold lines representing the maximum and minimum TG 1 limits;
- FIGURE 2-8 shows the softening point curves with digestion time of two crumb rubber modified bituminous blends or binders at 190-200°C;
- FIGURE 2-9 shows a graph of J nr values at 58°C for a base bituminous binder and J nr values of the corresponding crumb rubber modified bituminous binder or blend at various digestion time intervals;
- FIGURE 3-1 shows force ductility curves for a stiffness inducing and an elasticity inducing reactive elastomeric terpolymer;
- FIGURE 3-2 shows the average molar mass and molar mass distribution curves when a stiffness-inducing reactive elastomeric terpolymer additive is added to an over-digested crumb rubber modified bituminous binder;
- FIGURE 3-3 shows graphs of the softening point of an over-digested crumb rubber modified bituminous binder or blend before and after addition of a stiffness-inducing reactive elastomeric terpolymer (SI RET) additive in the form of an ethylene/n-butyl acrylate/glycidyl methacrylate composition;
- SI RET stiffness-inducing reactive elastomeric terpolymer
- FIGURE 3-4 shows J nr results at 58°C for an over-digested crumb rubber modified bituminous binder or blend before and after addition of a stiffness-inducing reactive elastomeric terpolymer (SI RET) additive in the form of an ethylene/n-butyl acrylate/glycidyl methacrylate composition;
- SI RET stiffness-inducing reactive elastomeric terpolymer
- FIGURE 3-5 shows Black diagrams of over-digested crumb rubber modified bituminous binders or blends before and after addition of a stiffness-inducing reactive elastomeric terpolymer (SI RET) additive in the form of an ethylene/n-butyl acrylate/glycidyl methacrylate composition;
- SI RET stiffness-inducing reactive elastomeric terpolymer
- FIGURE 4-1 shows graphs of average permanent strain accumulation vs. number of load cycles at 40°C, for an SBS mix, a repeat SBS mix, and a re-stiffened over-digested crumb rubber modified bituminous mix (MOD-CR mix); and
- FIGURE 4-2 shows graphs of average permanent strain accumulation vs. number of load cycles at 40°C, for a crumb rubber modified bituminous mix (CRM Mix) and a re-stiffened overdigested crumb rubber modified bituminous mix (MOD-CR mix).
- CCM Mix crumb rubber modified bituminous mix
- MOD-CR mix re-stiffened overdigested crumb rubber modified bituminous mix
- liquid non-particulate over-digested crumb rubber modified bituminous binders include ease of handling due to their lower viscosity, ease of blending with bitumen, and energy saving during processing.
- the challenge is to make sure that oils and/or low molecular weight compounds present in over-digested crumb rubber modified bituminous blends do not reduce the binder stiffness and offset the enhanced elastic properties imparted by the modifier.
- the rubber crumb surface texture/morphology is shown in the scanning electron microscope (SEM) photographs of Figure l-2(a)-(c).
- SEM scanning electron microscope
- the porous microstructures are consistent with comminution via an ambient process.
- the white spots seen in Figures l-2(b) and l-2(c) are most likely filler and not metal fragments since South Africa only imports non-steel reinforced tyres for rubber crumb manufacture (COLTO, 1998).
- the results for an elemental analysis of the rubber crumbs are shown in Table 1-1. They have a typical composition of carbon, oxygen, silicon, sulphur and traces of the metals, calcium, sodium, aluminium and zinc possibly from a vulcanization component.
- Table 1-1 Elemental composition (by weight) of the rubber crumbs
- Table 1-2 Crumb rubber modified bitumen properties for asphalt (A-Rl) and seals (S-Rl) according to South African national guidelines.
- the properties of rubber modified bituminous binders change with temperature, digestion time and energy consumed during the digestion process.
- the various stages (Stages 1 to 4) of crumb rubber modified bituminous blends or binders can be defined in terms of viscosity, as depicted in Figure 2-1 (obtained from Mturi G.A.J., O'Connell J., Zoorob S., De Beer M., "A study of crumb rubber modified bitumen used in South Africa", Road Materials and Pavement Design, Vol. 15, Issue 4, 2014, p. 774-790).
- Stage 1 is characterised by an initial increase in viscosity upon blending.
- the rubber particle dimension increases as the oil and/or lighter components of the bitumen diffuse into the three-dimensional rubber networks of poly-isoprene and polybutadiene linked by sulphur-sulphur bonds.
- the diffusion process varies according to the amount of cross-linkages in the rubber, the molecular compatibility between the rubber and the diffusing particles as well as the molecular weight of the latter.
- a further incorporation of the diffusing matter into the rubber particles would possibly occur as the sulphur-sulphur bonds start to thermally dissociate and this contributes to an additional increase in viscosity.
- the thermal dissociation process continues until a maximum viscosity point, referred to as Stage 1, is reached.
- the viscosity then decreases with digestion time in Stage 3 as the network disintegrates due to the loss of the sulphur linkages.
- the bitumen rubber is labelled as "over-digested", at least in South Africa.
- the decrease in viscosity continues until it reaches a point of relatively constant viscosity where the crumb robber modified bituminous blend is referred to as "terminal”. This has been depicted as Stage 4 in the digestion viscosity curve shown in Figure 2-1.
- the viscosity at Stage 4 is typically higher than the viscosity of the base bituminous binder. This viscosity increase is attributed to ageing (of the base bituminous binder) comingled with the incorporation of digested crumb rubber into the base bituminous binder.
- Stage 3 typically represents an application window or period for crumb rubber modified bituminous binders or blends.
- Lower application temperatures can increase this application window by slowing down the digestion process, as seen in Figure 2-2 (obtained from Muller J., Marais H., "The Perceived versus actual shelf-life and performance properties of bitumen rubber", Proceedings of the Asphalt Rubber Conference (Sousa J.B., ed.), 23-26 October 2012, Kunststoff, p. 429-441) where the lower viscosities of Stage 4 are delayed.
- this adds another complexity in that the effect of these extra constituents on asphalt performance needs to be investigated and controlled in guidelines and specifications.
- De-vulcanised over-digested crumb rubber modified bituminous binder is potentially less sensitive to handling conditions.
- the over-digested binder will still be a polymer modified binder and, hence, can give superior performance compared to standard unmodified penetration grade bitumen. It has been shown that significant resilience and elastic properties remain even after 32 hours of over-digestion for South African crumb rubber modified bituminous blends. This is confirmed through the analysis of PAV-aged (pressure aging vessel aged) crumb rubber modified bituminous binders (CRM binder) in Figure 2-3 (obtained from Mturi, G.A.J., O'Connell, J., & Anochie-Boateng, J.K. (2013).
- Figure 2-3 shows the recovered PAV-aged crumb rubber modified bituminous binder displaying elastic properties without the solvent insoluble crumb rubber. This is due to the increased incorporation (as a consequence of ageing/digestion) of de-linked polymers of the crumb rubber into the solventsoluble bitumen.
- the standard crumb rubber modified bituminous binder has viscosities within the set TG 1 limits (i.e. above 2000 mPa.s) up to 20 hours of digestion. Overdigestion during asphalt manufacture is therefore unlikely, and this binder would be expected to show relatively superior and acceptable performance in an asphalt mix.
- the two blends were incorporated in a standard medium continuously graded asphalt mix design and evaluated as per SABITA Manual 19, Guidelines for the design, manufacture and construction of bitumen rubber asphalt wearing courses, SABITA, Howard Place, South Africa, 2009 (hereinafter referred to as SABITA Manual 19, 2007).
- the mix design method was specifically developed for these crumb rubber modified bituminous binders.
- both crumb rubber modified asphalt mixes gave much poorer results from the expected performance and even inferior compared to a 50/70 penetration medium continuously graded asphalt mix (see Table 3-1).
- the crumb rubber modified asphalt mixes gave low Indirect Tensile Strength (ITS) and Marshall Stability test results with higher flow test values indicating increased susceptibility to deformation.
- the two crumb rubber modified asphalt mixes had similar gradings and the better performance of the standard crumb rubber modified bituminous binder was interestingly the higher viscosity binder.
- Table 3-1 Properties of medium continuous (MC) mix at optimum binder content
- Figure 2-7 shows softening points with digestion of the same two binders (CRM Bitumen 1 and CRM Bitumen 2) shown in Figure 2-5.
- the blend used in the nonflushing area (CRM Bitumen 1) had a much higher softening point than the required TG 1 (2007) maximum limit.
- the softening point of the blend from the flushing area (CRM Bitumen 2) (following blending) conformed to the set maximum criterion.
- the softening point of the flushing area blend fell below the minimum specification limit. This is precisely the time the blend conformed to the required application viscosity range in Figure 2-5.
- Figure 2-8 illustrates softening points with digestion of crumb rubber modified bituminous blends (CRM blend (CR1) and CRM blend (CR2)), re-blended with additional crumb rubber (CR) once over-digested.
- CCM blend CR1
- CRM blend CRM blend
- CR2 CRM blend
- CR crumb rubber modified bituminous blend
- the minimum softening points of the two over-digested crumb rubber modified bituminous blends and of the two re-blends (with digestion) were relatively similar, even though the digestion curves for the two crumb rubber types appeared slightly different. It can be considered that the softening points of the base bituminous binder and the over-digested bituminous binder (considered the base binder of the re-blend) act as limits preventing any further drop in softening points with continued digestion. This proves that the properties of the base binder are just as important in the manufacture of crumb rubber modified bituminous binders and can also be specified according to climatic conditions.
- MSCR multiple stress creep and recovery
- ASTM D7405 or AASHTO T350 evaluates the ability of binders to maintain elastic response at the stress levels of 100 Pa and 3200 Pa using a dynamic shear rheometer (DSR).
- DSR dynamic shear rheometer
- the test involves applying a 1-second creep loading followed by a 9-second recovery phase, and this constitutes a single cycle. At each stress level, 10 creep and recovery cycles are applied.
- the modified test procedure adopted for this investigation uses multiple stress levels of 25, 50, 100, 200, 400, 800, 1600, 3200, 6400, 12800 and 25600 Pa.
- the accumulation of J nr over time will eventually lead to permanent deformation.
- the MSCR test was modified to adopt multiple stress loading conditions because an in situ binder in an asphalt layer experiences a wide range of stresses from the passing of light to heavy vehicles. It is the higher stresses experienced under repetitive heavy vehicle loads that would eventually be responsible for pavement deformation. Therefore, it is at higher stress loading conditions that binders are better evaluated in terms of their damage resistance properties.
- Figure 2-9 shows the MSCR test results of the crumb rubber modified bituminous binders or blends.
- the test results graphically illustrated in Figure 2-9 show that the drop in crumb rubber modified bituminous binder or blend stiffness expected with digestion time is accompanied by an increase in stress sensitivity. Re-stiffening the over-digested crumb rubber modified bituminous binder with a modifier or additive should therefore be assessed as to whether it also improves stress resilience.
- Temporary network forming non-reactive additives e.g. fillers, styrene-butadiene- styrene, etc. were found unsuitable because they increased the stress sensitivity of overdigested crumb rubber modified bituminous binders.
- Reactive additives improved the stress resilience properties of over-digested crumb rubber modified bituminous binders.
- Elasticity-inducing additives e.g. terpolymers containing butyl acrylate at 28 wt% and glycidyl methacrylate at 5.3 wt%) had very little effect on stiffness properties of overdigested crumb rubber modified bituminous binder.
- Stiffness-inducing additives e.g. ethylene-vinyl acetate
- Stiffness-inducing additives had the highest effect on the stiffness of over-digested crumb rubber modified bituminous binders.
- Ethylene-vinyl acetate is however non-reactive in bituminous blends.
- SI(RET) reactive elastomeric terpolymers
- a terpolymer of ethylene, alkyl acrylate and glycidyl methacrylate (GMA) would be ideally suited for re-stiffening an over-digested crumb rubber modified bituminous binder.
- GMA reactive elastomeric terpolymers
- stiffness-inducing reactive elastomeric terpolymer to form polymer linkages with the over-digested crumb rubber modified bituminous binder (over digested CRM binder) was monitored through average molar mass and molar mass distribution determination, as shown in Figure 3-2.
- the stiffness-inducing reactive elastomeric terpolymer additive (SI RET) used was an ethylene/n-butyl acrylate/glycidyl methacrylate terpolymer (at 9% GMA).
- Figure 3-2 also shows the molar mass distribution of pure 70/100 penetration grade bitumen (Pure 10/100pen).
- the crumb rubber modified bituminous binder was prepared at temperatures between 190-200°C on a hot plate with a 4 bladed stainless-steel propeller (paddle stirrer) at a speed of 1500-2000rpm.
- the crumb rubber modified bituminous binder was maintained at this temperature until complete over digestion, notably where stable/consistent properties were achieved after 32-33 hours of stirring.
- 1% (m/m) SI RET additive was added to the over-digested blend without changing the stirring speed. The sample was stirred for a further 2 hours continuously. All blends were checked periodically and adjustments to the stirrer position done as the viscosity changed.
- PPA poly-phosphoric acid
- the SI RET additive increased the softening point (SP) of the over-digested binder (CRM blend (CR 1)) to a level similar to the original crumb rubber (CR) modified bituminous blend or binder. It also improved the storage stability of the re-stiffened blend as shown in Figure 3-3.
- the stiffness-inducing reactive elastomeric terpolymer additive and crumb rubber modified bituminous blend also exhibited improved stress resilience as shown in Figure 3-4 which shows graphs for the original crumb rubber modified bituminous binder (CRM binder (original)), the over-digested crumb rubber modified bituminous binder (over digested binder) and the stiffness-inducing reactive elastomeric terpolymer additive and crumb rubber modified bituminous blend (Over digested binder + SI RET), and increased stiffness and reduced elastic properties at high in-service temperatures (see Figure 3-5), when compared with over-digested crumb rubber modified bituminous binder (over digested binder).
- stiffness-inducing reactive elastomeric terpolymer additive and crumb rubber modified bituminous blend was found conforming to both A-Rl (for asphalt) and S-Rl (for seals) classes for all tested properties except viscosity at 190°C (as expected given it was over-digested), as shown in Table 3-1.
- Table 3-1 TGI (2015) properties of over-digested crumb rubber modified bituminous binder restiffened with a stiffness-inducing reactive elastomeric terpolymer (SI RET) additive.
- the stiffness-inducing reactive elastomeric terpolymer additive and crumb rubber modified bituminous blend or binder was investigated against a crumb rubber modified bituminous binder and a styrene-butadiene-styrene (SBS) modified bituminous binder in terms of permanent deformation resistance in asphalt mixes.
- Asphalt mixes were prepared using typical optimized mix designs used for road construction in South Africa, namely a bitumen rubber asphalt semi-open graded mix (BRASO) and a medium continuously graded mix (A-E2 SBS).
- the mixing and compaction of specimens were done in accordance with CSIR test protocols.
- the mixes were prepared using a heated mechanical mixer into which the calculated masses of aggregate and bituminous binder were placed. Aggregates were blended in accordance with the design grading. The materials were mixed for approximately 5 minutes or until a uniform mixture was obtained. After mixing, the material was placed in an oven set at compaction temperature for four hours to induce short-term ageing, after which the mix was compacted. Gyratory specimens for performance testing were compacted to a density of between 92 and 94 percent of the Maximum Theoretical Relative Density (MTRD). The resultant cored gyratory specimens were used to perform a repeated load permanent deformation (RLPD) test.
- MTRD Maximum Theoretical Relative Density
- the medium continuously graded mixes were prepared at the CSIR advanced road material testing laboratories using a standard SBS binder and an over-digested crumb rubber modified bituminous binder comprising SI RET additive (i.e. re-stiffened binder). Air voids and binder contents in the laboratory testing programme simulated the properties of the field mixes as best as possible. The original design was done using the Marshall Mix design method as per COLTO (1998) with the Interim Guidelines for the Design of Hot Mix Asphalt (2001). Table 4-1 shows the target binder and air voids contents as well as other volumetric properties of the mix.
- SI RET additive i.e. re-stiffened binder
- the densities were determined using the standard TMH1 C3 method.
- the results for the specimens tested are shown in Tables 4-2 and 4- 3 for the SBS mix (specimen 14383) and the re-stiffened binder (specimen 14706).
- the voids content for the performance tests specimens were within 6% to 8% voids content.
- Table 4-1 Summary of volumetric properties of the medium continuous mix
- Table 4-2 Gyratory specimens' densities (before and after coring) for the SBS mix
- Table 4-3 Gyratory specimens' densities (before and after coring) for the re-stiffened binder
- the UTM-25 test setup for dynamic modulus testing was used to conduct the test. Gyratory compacted specimens size of 100 mm diameter and 150mm high cored from cylindrical medium continuous specimens of 150 mm in diameter by 170 mm high were tested.
- the permanent deformation experimental design consisted of a single applied stress (deviator stress) level of 600 kPa at 40°C. The deviator stress was repeatedly pulsed in the vertical direction on the specimens using a haversine pulse load of 0.1 seconds and 0.9 seconds rest period until flow or 10,000 load cycles.
- Table 4-4 shows a summary of the test results that includes specimen air voids content, test temperatures, and the loading conditions. Specimens were tested at close to field voids.
- Figure 4-1 shows the average permanent strain accumulations in the test samples against the number of load applications at the applied deviator stress level of 600 kPa and test temperature of 40°C.
- the BRASO mixes were prepared at the CSIR advanced road material testing laboratories using a standard crumb rubber modified bituminous binder and an over-digested crumb rubber modified bituminous binder comprising SI RET additive (i.e. re-stiffened binder). Air voids and binder contents in the laboratory-testing programme simulated the properties of the field mixes as best as possible.
- the original design was done using the Marshall mix design method as per SABITA Manual 19, 2007 with the Interim Guidelines for the Design of Hot Mix Asphalt (2001). Table 4-5 shows the target binder and air voids contents as well as other design properties of the mix.
- the densities were determined using the standard TMH1 C3 method.
- the results for the specimens tested are shown in Tables 4-6 and 4- 7 for the crumb rubber modified bituminous mix (specimen 14536) and the re-stiffened mix respectively (specimen 14697).
- the voids content for the performance tests specimens were within 6% to 8% voids content.
- Table 4-6 Gyratory specimens densities (before and after coring) for the crumb rubber modified mix
- the permanent deformation experimental design consisted of a single applied stress (deviator stress) level of 276 kPa and 69kPa confinement pressure at 40°C.
- the deviator stress was repeatedly pulsed in the vertical direction on the specimens using a haversine pulse load of 0.1 seconds and 0.9 seconds rest period until flow or 10,000 load cycles.
- Table 4-8 shows a summary of the test results that include specimen air voids content, test temperatures, and the loading conditions. Specimens were tested at close to field voids.
- Figure 4-2 shows the average permanent strain accumulations in the test samples against the number of load applications at the applied deviator stress level of 276 kPa with a confining pressure of 69kPa and test temperature of 40°C.
- the re-stiffened over-digested crumb rubber modified bituminous mix showed better permanent deformation resistance than the standard crumb rubber modified bituminous mix at the tested temperature.
- the invention provides a method to re-stiffen over-digested rubber modified bituminous binders or blends.
- Over-digested rubber modified bituminous blends restiffened with a stiffness-inducing reactive elastomeric terpolymer additive advantageously produced stiffer, stable and stress resilient homogeneous modified blends.
- HMA Hot Mix Asphalt
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Civil Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Road Paving Structures (AREA)
Abstract
A method of re-stiffening an over-digested rubber modified bituminous binder includes admixing a reactive, stiffness inducing organic additive with the over-digested rubber modified bituminous binder to produce a re-stiffened rubber modified bituminous binder with an increased softening point. Typically, the re-stiffened rubber modified bituminous binder exhibits an improved Jnr, an improved storage stability, and an improved stress resilience. The admixing takes place at an elevated temperature of at least 185°C. The invention also provides a rubber modified bituminous binder that includes a digested rubber bituminous admixture with a softening point of at least 55°C and a dynamic viscosity at 190°C of less than 2000 mPa.s. The rubber modified bituminous binder is suitable for both asphalt and seal surfacing applications. The invention extends to a method of sealing or paving a surface that includes applying a layer which includes a rubber modified bituminous binder to the surface, the rubber modified bituminous binder being in the form of a digested rubber bitumen admixture with a softening point of at least 55°C and a dynamic viscosity at 190°C of less than 2000 mPa.s.
Description
RUBBER MODIFIED BITUMINOUS BINDERS
This Invention relates to rubber modified bituminous binders. In particular, the invention relates to a method of re-stiffening an over-digested rubber modified bituminous binder, to a rubber modified bituminous binder, and to a method of sealing or asphalt paving a surface.
In for example South Africa, crumb rubber modified bituminous binder has historically been manufactured in a wet process to a criteria as set out in a document known as Technical Guideline (TG 1), The Use of Modified Bituminous Binders in Road Construction (Third Edition), SABITA, Howard Place, South Africa, 2015, ISBN 978-1-874968-67-2 (hereinafter referred to as TGI, 2015) through blending penetration grade bitumen (72 - 82 % by mass), rubber crumbs (18 - 24 % by mass) and extender oil or high boiling point fluxing agents (0 - 4 % by mass) at elevated temperatures of typically between 190 - 210°C. The blending is done by a high-speed stirring device for 1 to 4 hours until the bitumen is considered modified.
The typical base bitumen or base bituminous binder conventionally used in South Africa was the 70/100 penetration grade bitumen conforming to the requirements of South African National Standard 4001-BT1 [SANS 4001-BT1], 2014. Penetration Grade Bitumens (Edition 1.2). South Africa: Standards South Africa (hereinafter referred to as SANS 4001-BT1, 2014). Historically, the extender oil was produced as per the requirements of the Committee of Land Transport Officials ([COLTO] (1998), Standard Specifications for Road and Bridge Works for State Road Authorities (1998 Edition), South Africa: South African Institution of Civil Engineering) (hereinafter referred to as COLTO, 1998). Rubber crumbs of the grading requirements stated in TGI, 2015 are recommended. The rubber crumb particles essentially pass a 1.00 mm sieve (1.18 mm was the requirement in a previous guideline document i.e., TGI, 2007) and the majority is retained on a 0.6 mm sieve.
In the wet process of using crumb rubber to modify asphalt mixes, the crumb rubber is thus digested in bitumen using a combination of high temperatures, agitation and
controlled digestion times. This produces rubber modified bitumen with enhanced elastic properties that can contain up to 25% rubber digested in bitumen. The limitations of this production route have historically been the high handling temperatures, the heterogeneous nature of rubber modified bituminous binder material and the limited window period of application for these binder materials to have optimum performance.
In South Africa, rubber modified bituminous blends used to be tested according to the methods and requirements in TG 1, 2015. TG 1, 2015 has a minimum viscosity requirement of 2000 mPa.s (or 20 dPa.s) for rubber modified bituminous binder grades used in sealing (grade S-Rl) and asphalt mix (grade A-Rl) applications. Traditionally, when rubber modified bituminous blends are over-digested and their viscosity fall below the minimum specification, their further usage is restricted to blending them into new batches of rubber modified bituminous binder up to a maximum proportion of 20% by mass of over-digested binder. Although rubber modified bituminous binders have been used successfully in South Africa for the past 25 years, a constant challenge for asphalt/seal manufacturers is that the rate of disposal of the over-digested binder is often less than the rate of accumulation of the over-digested binder, aggravated at times of inclement weather.
According to one aspect of the invention, there is provided a method of restiffening an over-digested rubber modified bituminous binder, the method including admixing a reactive, stiffness inducing organic additive with the over-digested rubber modified bituminous binder to produce a re-stiffened rubber modified bituminous binder with an increased softening point, wherein the admixing takes place at an elevated temperature of at least 185°C.
Typically, the re-stiffened rubber modified bituminous binder also exhibits an improved Jnr. An improved Jnr is a Jnr value, in kPa -1, for the re-stiffened rubber modified bituminous binder, which is lower than said Jnr value, in kPa -1, for the over-digested rubber modified bituminous binder, over a stress range of at least 100- 10000 Pa, using a multiple stress creep and recovery test.
The re-stiffened rubber modified bituminous binder typically also exhibits an improved storage stability. An improved storage stability is a storage stability value, in °C, for the re-stiffened rubber modified bituminous binder, which is lower than said storage stability value, in °C, for the over-digested rubber modified bituminous binder using a storage stability of polymer modified binders (TGI MB-6) test.
The re-stiffened rubber modified bituminous binder typically also exhibits an improved stress resilience. An improved stress resilience is Jnr values, in kPa -1, for the re-stiffened rubber modified bituminous binder, which display a lower change with increased stress than said Jnr values, in kPa -1, for the over-digested rubber modified bituminous binder, over a stress range of at least 100 - 10000 Pa, using a multiple stress creep and recovery test.
In this specification, an over-digested rubber modified bituminous binder is a rubber modified bituminous binder with a viscosity at 190°C of less than 2000 mPa.s and/or with a softening point of less than 55°C.
Preferably, the over-digested rubber modified bituminous binder is completely over-digested. A completely over-digested rubber modified bituminous binder is an overdigested rubber modified bituminous binder whose viscosity approaches that of a base bituminous binder of the rubber modified bituminous binder, once the viscosity has dropped below 2000 mPa.s, and/or a completely over-digested rubber modified bituminous binder is an over-digested rubber modified bituminous binder whose softening point approaches that of the base binder, once the softening point has dropped below 55°C.
If necessary, the method of the invention may include digesting the over-digested rubber modified bituminous binder for a period of time sufficient to ensure that the overdigested rubber modified bituminous binder is completely over-digested, prior to admixing the reactive, stiffness inducing organic additive with the over-digested rubber modified bituminous binder.
The rubber in the rubber modified bituminous binder may be crumb rubber. The crumb rubber may be as hereinbefore described, e.g. in accordance with TG 1, 2015.
The bitumen in the rubber modified bituminous binder may include a base bitumen as hereinbefore described and the rubber modified bituminous binder, prior to becoming over-digested, may be prepared in accordance with the guidelines set out in TG 1, 2015. The rubber modified bituminous binder may thus include an extender oil or high boiling point fluxing agents.
The reactive, stiffness inducing organic additive may be reactive in the sense that reactions between one or more components of the reactive, stiffness inducing organic additive react(s) with functional groups present in the over-digested rubber modified bituminous binder to produce a re-stiffened rubber modified bituminous binder with an altered composition and an increased softening point.
In one embodiment of the method of the invention, these reactions provide an increase (compared to over-digested rubber modified bituminous binder) in weight fraction of components of the re-stiffened rubber modified bituminous binder with a molar mass over at least part of a molar mass range between 2xl06 and 8xl06 g/mol, or between 2xl06 and 7xl06 g/mol, or between 3xl06 and 8xl06 g/mol or between 3X106 and 7xl06 g/mol, e.g. between 4xl06 and 6xl06 g/mol.
The reactive, stiffness inducing organic additive may be reactive in the sense that reactions between one or more components of the reactive, stiffness inducing organic additive react(s) with functional groups (e.g. carboxylic acid functional groups) present in the overdigested rubber modified bituminous binder to produce a re-stiffened rubber modified bituminous binder with an improved Jnr, and/or an improved storage stability and/or an improved stress resilience.
The reactive, stiffness inducing organic additive may be a reactive elastomeric organic additive.
The reactive, stiffness inducing organic additive may be a reactive elastomeric polymer composition.
The reactive, stiffness inducing organic additive may be a reactive elastomeric terpolymer composition. The terpolymer composition may include ethylene as a monomer. Instead, or in addition, the terpolymer may include an alkyl acrylate as a monomer. Instead, or in addition, the terpolymer may include glycidyl methacrylate as a monomer.
In one embodiment of the invention, the reactive elastomeric terpolymer is a terpolymer of ethylene, an alkyl acrylate and glycidyl methacrylate. An example of such a terpolymer is a reactive stiffness inducing terpolymer of ethylene/n-butyl acrylate/glycidyl methacrylate. The glycidyl methacrylate may be present in a concentration of about 9% by mass.
The admixing of the reactive, stiffness inducing organic additive with the overdigested rubber modified binder should be in the absence of poly-phosphoric acid. When admixed in the presence of poly-phosphoric acid, which is often used with products such as a terpolymer composition of ethylene/n-butyl acrylate/glycidyl methacrylate, the inventor surprisingly found that the poly-phosphoric acid had a negative effect on the desired properties of the re-stiffened rubber modified bituminous binder.
Preferably, the admixing takes place at an elevated temperature of between about 185°C and about 210°C, more preferably between about 190°C and about 200°C, most preferably between about 190°C and about 195°C, e.g. at about 193°C.
The admixing may be for less than about 160 minutes, preferably less than about 145 minutes, more preferably less than about 130 minutes, e.g. about 120 minutes.
The admixing may be for at least about 100 minutes, preferably at least about 110 minutes, more preferably at least about 120 minutes.
The re-stiffened rubber modified bituminous binder may have an increased softening point to at least 56°C, preferably to at least 58°C, more preferably to at least 60°C, e.g. to at least 61°C.
The re-stiffened rubber modified bituminous binder may show a reduction in elasticity with an increase in the complex modulus (G*), as evidenced by reduced phase angles at high in-service temperatures. This can best be seen on a Black diagram plot of complex modulus versus phase angle, at various frequencies and in-service temperatures, using data from a dynamic shear rheometer.
With high in-service temperatures is meant a temperature at which the restiffened rubber modified bituminous binder would normally be used to resist deformation, e.g. when an asphalt road carries traffic in a hot summer season, i.e. at temperatures in the range of between about 20°C and about 70°C.
The stiffness inducing organic additive and the over-digested rubber modified binder may be admixed in a mass ratio of between about 0.5:99.5 and about 2.0:98.0, preferably between about 0.5:99.5 and about 1.5:98.5, more preferably between about 0.8:99.2 and about 1.2:98.8, e.g. about 1.0:99.0.
The invention extends to a re-stiffened rubber modified bituminous binder when produced by the method of re-stiffening an over-digested rubber modified bituminous binder as hereinbefore described.
The re-stiffened rubber modified bituminous binder may have a softening point of at least 56°C, preferably at least 58°C, more preferably at least 60°C, e.g. at least 61°C.
In one embodiment of the re-stiffened rubber modified bituminous binder produced by the method of re-stiffening an over-digested rubber modified bituminous binder, the re-stiffened rubber modified bituminous binder has an increased weight fraction (compared to over-digested rubber modified bituminous binder) of components of the re-stiffened rubber modified bituminous binder with a molar mass over at least part of a molar mass range between 2xl06 and 8xl06 g/mol, or between 2xl06 and 7xl06 g/mol, or between 3xl06 and 8xl06 g/mol or between 3X106 and 7xl06 g/mol, e.g. between 4xl06 and 6xl06 g/mol.
The re-stiffened rubber modified bituminous binder produced by the method of re-stiffening an over-digested rubber modified bituminous binder may have a dynamic viscosity at 190°C of less than about 2000 mPa.s, or less than about 1500 mPa.s, or less than about 1200 mPa.s, or less than about 1000 mPa.s, or less than about 900 mPa.s, e.g. about 800 mPa.s. As will be appreciated, the dynamic viscosity of the re-stiffened rubber modified bituminous binder will depend on the formulation thereof, and on the reactive, stiffness inducing organic additive used.
Preferably, the re-stiffened rubber modified bituminous binder has a dynamic viscosity at 190°C of at least 100 mPa.s.
According to another aspect of the invention, there is provided a rubber modified bituminous binder, the binder including a digested rubber bituminous admixture with a softening point of at least 55°C and a dynamic viscosity at 190°C of less than 2000 mPa.s.
Preferably, the rubber modified bituminous binder has a softening point of at least 56°C, more preferably at least 58°C, most preferably at least 60°C, e.g. at least 61°C. As will be appreciated, the softening point will depend on the formulation of the rubber modified bituminous binder.
The rubber modified bituminous binder may have a dynamic viscosity at 190°C of less than about 1500 mPa.s, or less than about 1200 mPa.s, or less than about 1000 mPa.s, or less than about 900 mPa.s, e.g. about 800 mPa.s. As will be appreciated, the dynamic viscosity will depend on the formulation of the rubber modified bituminous binder.
Preferably, the rubber modified bituminous binder has a dynamic viscosity at 190°C of at least 100 mPa.s.
The rubber modified bituminous binder, or the re-stiffened rubber modified bituminous binder, may have a compression recovery at 5 minutes, according to the MB-ll test method as set out in TG 1, 2015, of more than 70%, or more than 80%. As will be appreciated,
the compression recovery at 5 minutes will depend on the formulation of the rubber modified bituminous binder.
The rubber modified bituminous binder, or the re-stiffened rubber modified bituminous binder, may have a compression recovery after 1 hour, according to the MB-ll test method, of more than 70%, preferably more than 75%, more preferably more than 80%, e.g. 85.6%. As will be appreciated, the compression recovery after 1 hour will depend on the formulation of the rubber modified bituminous binder
The rubber modified bituminous binder, or the re-stiffened rubber modified bituminous binder, may have a compression recovery after 24 hours, according to the MB-ll test method, of more than 40%, preferably more than 50%, more preferably more than 60, e.g. 69.9. As will be appreciated, the compression recovery after 24 hours will depend on the formulation of the rubber modified bituminous binder.
The rubber modified bituminous binder, or the re-stiffened rubber modified bituminous binder, may have a compression recovery after 4 days, according to the MB-ll test method, of more than 40, preferably more than 50%, more preferably more than 60%, e.g. 67.9%. As will be appreciated, the compression recovery after 4 days hours will depend on the formulation of the rubber modified bituminous binder.
The rubber modified bituminous binder, or the re-stiffened rubber modified bituminous binder, may have a resilience at 25°C, according to the MB-10 test method as set out in TG 1, 2015, of more than 13%, preferably more than 14%, more preferably more than 15%, e.g. 17.3%. As will be appreciated, the resilience at 25°C will depend on the formulation of the rubber modified bituminous binder.
The rubber modified bituminous binder, or the re-stiffened rubber modified bituminous binder, may flow, according to the MB-12 test method as set out in TG 1, 2015, more than 10mm, or more than 15mm, preferably more than 20mm, more preferably more than 25mm, e.g. 28mm. As will be appreciated, the flow will depend on the formulation of the rubber modified bituminous binder.
In one embodiment of the invention, the rubber modified bituminous binder, or the re-stiffened rubber modified bituminous binder, has a weight fraction of at least about 0.13, preferably at least about 0.15, more preferably at least about 0.18, most preferably at least about 0.2 of components with an average molar mass between 3.9xl06 g/mol and 4.1xl06 g/mol.
In one embodiment of the invention, the rubber modified bituminous binder, or the re-stiffened rubber modified bituminous binder, has a weight fraction of at least about 0.13, preferably at least about 0.15, more preferably at least about 0.18, most preferably at least about 0.2 of components with an average molar mass between 4.1xl06 g/mol and 4.2xl06 g/mol. As will be appreciated, said weight fraction will depend on the formulation of the rubber modified bituminous binder.
The rubber modified bituminous binder, or the re-stiffened rubber modified bituminous binder, may include reaction products from reactions between glycidyl methacrylate and functional groups of the over-digested bituminous binder (e.g. carboxylic acid groups).
The rubber modified bituminous binder may be produced by a method of restiffening an over-digested rubber modified bituminous binder as hereinbefore described.
The rubber modified bituminous binder may be produced from over-digested rubber modified bituminous binder. The over-digested rubber modified bituminous binder may be as hereinbefore described.
The rubber in the rubber modified bituminous binder may be crumb rubber.
The rubber modified bituminous binder, or the re-stiffened rubber modified bituminous binder, may be for use as a surface seal in a method of sealing a surface.
The rubber modified bituminous binder, or the re-stiffened rubber modified bituminous binder, may be for use as a binder in an asphalt mix for asphalt paving a surface.
According to a further aspect of the invention, there is provided a method of sealing or asphalt paving a surface, the method including applying a layer which includes a rubber modified bituminous binder to the surface, the rubber modified bituminous binder being in the form of a digested rubber bitumen admixture with a softening point of at least 55°C and a dynamic viscosity at 190°C of less than 2000 mPa.s.
The layer typically includes aggregate particles, particularly when the method is an asphalt paving method. The rubber modified bituminous binder and the aggregate particles thus may a seal surfacing layer or a layer of an asphalt mix. The method of sealing or asphalt paving a surface may thus be a method of paving a surface with asphalt or an asphalt mix, sometimes referred to as asphalt concrete.
The asphalt mix may be a medium continuously graded mix and may have a maximum displacement (using a Universal Testing Machine test setup, i.e. a UTM-25 test setup for dynamic modulus testing, with gyratory compacted specimens size of 100 mm diameter and 150mm high cored from cylindrical medium continuous specimens of 150 mm in diameter by 170 mm high, a single applied stress (deviator stress) level of 276 kPa and 69kPa confinement pressure at 40°C, with the deviator stress repeatedly pulsed in the vertical direction on the specimens using a haversine pulse load of 0.1 seconds and 0.9 seconds rest period until flow or 10,000 load cycles) equal to an identical asphalt SBS mix (in terms of mix design, grading, aggregate type and binder content) based on an A-E2 conforming SBS binder, preferably better than (e.g. at least 25% better), more preferably notably better than (e.g. at least 50% better), most preferably more than double, the performance, e.g. 1.6-2.6mm as opposed to 7.3-7.6mm, of the identical asphalt SBS mix.
The asphalt mix may be a medium continuously graded mix and may have a flow number (using a UTM-25 test setup for dynamic modulus testing, with gyratory compacted specimens size of 100 mm diameter and 150mm high cored from cylindrical medium continuous specimens of 150 mm in diameter by 170 mm high, a single applied stress (deviator stress) level of 276 kPa and 69kPa confinement pressure at 40°C, with the deviator stress repeatedly pulsed in the vertical direction on the specimens using a haversine pulse load of 0.1 seconds and 0.9 seconds rest period until flow or 10,000 load cycles) equal to an identical asphalt SBS mix (in
terms of mix design, grading, aggregate type and binder content) based on an A-E2 conforming SBS binder, preferably better than (e.g. at least 25% better), more preferably notably better than (e.g. at least 50% better), most preferably more than double, the performance, e.g. 5700-8700 as opposed to 900-2000, of the identical asphalt SBS mix.
The asphalt mix may be a bitumen-rubber asphalt semi-open (BRASO) graded mix and may have a maximum displacement (using a UTM-25 test setup for dynamic modulus testing, with gyratory compacted specimens size of 100 mm diameter and 150mm high cored from cylindrical medium continuous specimens of 150 mm in diameter by 170 mm high, a single applied stress (deviator stress) level of 276 kPa and 69kPa confinement pressure at 40°C, with the deviator stress repeatedly pulsed in the vertical direction on the specimens using a haversine pulse load of 0.1 seconds and 0.9 seconds rest period until flow or 10,000 load cycles) equal to an identical asphalt mix (in terms of mix design, grading, aggregate type and binder content) based on an A-Rl conforming crumb rubber modified bituminous binder, preferably better than (e.g. at least 25% better), more preferably notably better than (e.g. at least 50% better), most preferably more than double, the performance, e.g. 0.7-1.1mm as opposed to 3.5-7.5mm, of the identical asphalt mix based on an A-Rl conforming crumb rubber modified bituminous binder.
The asphalt mix may be a bitumen-rubber asphalt semi-open (BRASO) graded mix and may have a flow number (using a UTM-25 test setup for dynamic modulus testing, with gyratory compacted specimens size of 100 mm diameter and 150mm high cored from cylindrical medium continuous specimens of 150 mm in diameter by 170 mm high, a single applied stress (deviator stress) level of 276 kPa and 69kPa confinement pressure at 40°C, with the deviator stress repeatedly pulsed in the vertical direction on the specimens using a haversine pulse load of 0.1 seconds and 0.9 seconds rest period until flow or 10,000 load cycles) equal to an identical asphalt mix (in terms of mix design, grading, aggregate type and binder content) based on an A- R1 conforming crumb rubber modified bituminous binder, preferably better than (e.g. at least 25% better), more preferably notably better than (e.g. at least 50% better), most preferably more than double, the performance, e.g. 7400-8800 as opposed to 1400-4200, of the identical asphalt mix based on an A-Rl conforming crumb rubber modified bituminous binder.
The rubber modified bituminous binder may be as hereinbefore described.
The aggregate particles may be conventional aggregate particles e.g. used in paving, such as road construction, and the ratio of rubber modified bituminous binder and aggregate particles in the layer may be entirely conventional.
The invention will now be described in more detail with reference to the accompanying drawings in which
FIGURE 1-1 shows a graph of the size grading of crumb rubber particles used in studies conducted by the inventor;
FIGURE 1-2 shows scanning electron microscope (SEM) photographs of the rubber crumbs, illustrating the surface texture/morphology of the rubber crumbs;
FIGURE 2-1 shows a typical digestion viscosity curve of crumb rubber modified bituminous binder;
FIGURE 2-2 shows digestion viscosity curves of crumb rubber modified bituminous binders or blends at different handling temperatures, as a function of time;
FIGURE 2-3 shows a Black diagram of crumb rubber modified bituminous binder (CRM binder) with PAV-ageing before and after solvent-soluble recovery;
FIGURE 2-4 shows digestion viscosity curves of two crumb rubber modified bituminous binders or blends at 190-200°C, as a function of time;
FIGURE 2-5 shows digestion viscosity curves of two crumb rubber modified bituminous binders or blends based on base binders from different refineries at 190-200°C as a function of time, with the solid bold horizontal lines representing the maximum and minimum TG 1 limits;
FIGURE 2-6 shows a photographs of non-flushing (CRM bitumen 1) and flushing (CRM bitumen 2) areas;
FIGURE 2-7 shows softening point curves with digestion time of crumb rubber modified bituminous blends or binders at 190-200°C, with the solid bold lines representing the maximum and minimum TG 1 limits;
FIGURE 2-8 shows the softening point curves with digestion time of two crumb rubber modified bituminous blends or binders at 190-200°C;
FIGURE 2-9 shows a graph of Jnr values at 58°C for a base bituminous binder and Jnr values of the corresponding crumb rubber modified bituminous binder or blend at various digestion time intervals;
FIGURE 3-1 shows force ductility curves for a stiffness inducing and an elasticity inducing reactive elastomeric terpolymer;
FIGURE 3-2 shows the average molar mass and molar mass distribution curves when a stiffness-inducing reactive elastomeric terpolymer additive is added to an over-digested crumb rubber modified bituminous binder;
FIGURE 3-3 shows graphs of the softening point of an over-digested crumb rubber modified bituminous binder or blend before and after addition of a stiffness-inducing reactive elastomeric terpolymer (SI RET) additive in the form of an ethylene/n-butyl acrylate/glycidyl methacrylate composition;
FIGURE 3-4 shows Jnr results at 58°C for an over-digested crumb rubber modified bituminous binder or blend before and after addition of a stiffness-inducing reactive elastomeric terpolymer (SI RET) additive in the form of an ethylene/n-butyl acrylate/glycidyl methacrylate composition;
FIGURE 3-5 shows Black diagrams of over-digested crumb rubber modified bituminous binders or blends before and after addition of a stiffness-inducing reactive elastomeric terpolymer (SI RET) additive in the form of an ethylene/n-butyl acrylate/glycidyl methacrylate composition;
FIGURE 4-1 shows graphs of average permanent strain accumulation vs. number of load cycles at 40°C, for an SBS mix, a repeat SBS mix, and a re-stiffened over-digested crumb rubber modified bituminous mix (MOD-CR mix); and
FIGURE 4-2 shows graphs of average permanent strain accumulation vs. number of load cycles at 40°C, for a crumb rubber modified bituminous mix (CRM Mix) and a re-stiffened overdigested crumb rubber modified bituminous mix (MOD-CR mix).
The inventor believes that although digestion viscosity curves have been used successfully as a production tool, they cannot be used as an indicator of performance of rubber modified bituminous binders because viscosity is tested at much higher handling temperatures not representative of actual field performance at lower in-service temperatures (e.g. temperatures of 20°C - 70°C). Rheologically, disintegrated rubber polymers from the devulcanization of the rubber crumbs present after over-digestion are still capable of imparting elastic properties. Over-digested crumb rubber modified bituminous binder should remain useful for re-blending or continual usage in alternative products given appropriate
characterisation. In addition, the potential benefits of liquid non-particulate over-digested crumb rubber modified bituminous binders include ease of handling due to their lower viscosity, ease of blending with bitumen, and energy saving during processing. The challenge is to make sure that oils and/or low molecular weight compounds present in over-digested crumb rubber modified bituminous blends do not reduce the binder stiffness and offset the enhanced elastic properties imparted by the modifier. The inventor thus reviewed earlier studies conducted to investigate the properties of crumb rubber modified bituminous binders (see Mturi GAJ, O'Connell J, Marais H and Hawes N, A Brief Analysis of Over-Digested Crumb Rubber Modified Bitumen, Rubberized Asphalt: Asphalt Rubber Conference (2015) 409-419, Las Vegas, United States of America) and proceeded to propose methods by which over-digested crumb rubber modified bituminous binders can be re-stiffened.
In these studies, the typical 70/100 penetration grade bitumen conforming to SANS 4001-BT1, 2014 was used. An extender oil produced as per the requirements of COLTO, 1998 was used with the bitumen. Rubber crumbs of the grading requirements stated in TGI, 2015 were used. The rubber crumb particles used in the studies essentially pass a 1.00 mm sieve (1.18 mm was the requirement in a previous guideline document i.e. TGI, 2007) and the majority is retained on a 0.6 mm sieve. Figures 1-1 and 1-2 (obtained from Mturi, G., Zoorob, S.E., O'Connell, J., Anochie-Boateng, J., & Maina, J. (2011b). Rheological testing of crumb rubber modified bitumen. In Proceedings of the 7th International Committee on Road & Airfield Pavement Technology (pp. 1316-1327). Bangkok, Thailand, paper P18) depict the grading for the rubber crumbs used in this investigation.
The rubber crumb surface texture/morphology is shown in the scanning electron microscope (SEM) photographs of Figure l-2(a)-(c). The porous microstructures are consistent with comminution via an ambient process. The white spots seen in Figures l-2(b) and l-2(c) are most likely filler and not metal fragments since South Africa only imports non-steel reinforced tyres for rubber crumb manufacture (COLTO, 1998). The results for an elemental analysis of the rubber crumbs are shown in Table 1-1. They have a typical composition of carbon, oxygen, silicon, sulphur and traces of the metals, calcium, sodium, aluminium and zinc possibly from a vulcanization component.
Table 1-1: Elemental composition (by weight) of the rubber crumbs
SPECTRUM C O Si S Ca Na Al Zn Total
Sample 1 81.93 16.60 0.91 0.55 100.00
Sample 1 R 76.54 23.46 <0.005 100.00
1
Sample 1 R 86.42 11.19 0.58 1.36 0.44 <0.005 100.00
2
Sample 1 R 85.91 11.52 2.08 0.50 <0.005 100.00
3
Sample 1 R 88.71 8.02 0.75 2.03 0.51 <0.005 100.00
4
Max. Dete 88.71 23.46 0.75 2.08 0.44 0.55 0.51 <0.005
The test results in Table 1-2 below indicate that crumb rubber modified bituminous blends used in this investigation conformed to South African Technical Guideline 1 guidelines for the A-Rl grade, which is an asphalt grade (TGI, 2015), except that the resilience of crumb rubber modified bituminous binder 1 was slightly above recommendation. The grade S- R1 is a surfacing seal grade. The test methods indicated with an MB in the name of the test method are described in TGI, 2015.
Table 1-2: Crumb rubber modified bitumen properties for asphalt (A-Rl) and seals (S-Rl) according to South African national guidelines.
Class Results Test
PROPERTY Unit (TGI, 2015)
_ Method _ Binder 1 Binder 2 S-Rl A-Rl
Softening Point °C 62.8 65.0 MB-17 55-65 55-65
Dynamic Viscosity at dPa.s
35 45 MB-13 20-40 20-50
190°C
Compression
Recovery after
5 mins 86.6 84.6 MB-11 >70 >80
1 hour % 88.6 88.6 >70 >70
24 N/A 80.7 >40 N/A hours
Resilience at 25°C % 42 32 MB-10 13-35 13-40
Flow mm 14 17 MB-12 15-70 10-50
The properties of rubber modified bituminous binders change with temperature, digestion time and energy consumed during the digestion process. The various stages (Stages 1 to 4) of crumb rubber modified bituminous blends or binders can be defined in terms of viscosity, as depicted in Figure 2-1 (obtained from Mturi G.A.J., O'Connell J., Zoorob S., De Beer M., "A study of crumb rubber modified bitumen used in South Africa", Road Materials and Pavement Design, Vol. 15, Issue 4, 2014, p. 774-790).
Stage 1 is characterised by an initial increase in viscosity upon blending. In this stage, the rubber particle dimension increases as the oil and/or lighter components of the bitumen diffuse into the three-dimensional rubber networks of poly-isoprene and polybutadiene linked by sulphur-sulphur bonds. The diffusion process varies according to the amount of cross-linkages in the rubber, the molecular compatibility between the rubber and the diffusing particles as well as the molecular weight of the latter. A further incorporation of the diffusing
matter into the rubber particles would possibly occur as the sulphur-sulphur bonds start to thermally dissociate and this contributes to an additional increase in viscosity.
The thermal dissociation process continues until a maximum viscosity point, referred to as Stage 1, is reached. The viscosity then decreases with digestion time in Stage 3 as the network disintegrates due to the loss of the sulphur linkages. Once the viscosity reaches the minimum recommended viscosity limit of 20 dPa.s (or 2000 mPa.s) in TGI, 2015, the bitumen rubber is labelled as "over-digested", at least in South Africa. The decrease in viscosity continues until it reaches a point of relatively constant viscosity where the crumb robber modified bituminous blend is referred to as "terminal". This has been depicted as Stage 4 in the digestion viscosity curve shown in Figure 2-1.
The viscosity at Stage 4 is typically higher than the viscosity of the base bituminous binder. This viscosity increase is attributed to ageing (of the base bituminous binder) comingled with the incorporation of digested crumb rubber into the base bituminous binder.
Stage 3 typically represents an application window or period for crumb rubber modified bituminous binders or blends. Lower application temperatures can increase this application window by slowing down the digestion process, as seen in Figure 2-2 (obtained from Muller J., Marais H., "The Perceived versus actual shelf-life and performance properties of bitumen rubber", Proceedings of the Asphalt Rubber Conference (Sousa J.B., ed.), 23-26 October 2012, Munich, p. 429-441) where the lower viscosities of Stage 4 are delayed. This has led to the development of warm mix additives to allow for the application of these binders at lower temperatures. However, this adds another complexity in that the effect of these extra constituents on asphalt performance needs to be investigated and controlled in guidelines and specifications.
De-vulcanised over-digested crumb rubber modified bituminous binder is potentially less sensitive to handling conditions. The over-digested binder will still be a polymer modified binder and, hence, can give superior performance compared to standard unmodified penetration grade bitumen. It has been shown that significant resilience and elastic properties remain even after 32 hours of over-digestion for South African crumb rubber modified
bituminous blends. This is confirmed through the analysis of PAV-aged (pressure aging vessel aged) crumb rubber modified bituminous binders (CRM binder) in Figure 2-3 (obtained from Mturi, G.A.J., O'Connell, J., & Anochie-Boateng, J.K. (2013). Limitations of current South African test methods for bituminous binders. Construction and Building Materials, 45, 314-323) which were shown to still exhibit a certain degree of elastic properties. Figure 2-3 also shows the recovered PAV-aged crumb rubber modified bituminous binder displaying elastic properties without the solvent insoluble crumb rubber. This is due to the increased incorporation (as a consequence of ageing/digestion) of de-linked polymers of the crumb rubber into the solventsoluble bitumen.
Over-digestion results in a decrease in viscosity, so previous investigators (O'Connell J., Anochie-Boateng J., Marais H., "Evaluation of bitumen-rubber asphalt manufactured from modified binder at lower viscosity", Proceedings of the 29th Southern African Transport Conference, 16-19 August 2010, Pretoria, p. 129-138) investigated two crumb rubber modified bituminous blends, one conforming to TG 1 guideline requirements and the other overdigested such that the viscosity is below the current range in the TG 1 guideline. The digestion viscosity curves of the two crumb rubber modified bituminous blends or binders (CRM binders) are shown in Figure 2-4. Both blends do not show significant viscosity changes during the shortterm digestion conditions. The standard crumb rubber modified bituminous binder has viscosities within the set TG 1 limits (i.e. above 2000 mPa.s) up to 20 hours of digestion. Overdigestion during asphalt manufacture is therefore unlikely, and this binder would be expected to show relatively superior and acceptable performance in an asphalt mix.
The two blends were incorporated in a standard medium continuously graded asphalt mix design and evaluated as per SABITA Manual 19, Guidelines for the design, manufacture and construction of bitumen rubber asphalt wearing courses, SABITA, Howard Place, South Africa, 2009 (hereinafter referred to as SABITA Manual 19, 2007). The mix design method was specifically developed for these crumb rubber modified bituminous binders. Interestingly, both crumb rubber modified asphalt mixes gave much poorer results from the expected performance and even inferior compared to a 50/70 penetration medium continuously graded asphalt mix (see Table 3-1). The crumb rubber modified asphalt mixes gave low Indirect Tensile Strength (ITS) and Marshall Stability test results with higher flow test values indicating increased
susceptibility to deformation. The two crumb rubber modified asphalt mixes had similar gradings and the better performance of the standard crumb rubber modified bituminous binder was interestingly the higher viscosity binder.
Mturi et al. (Mturi, G., Conrad, S., & Mogonedi, K. (2011). JR 5023: Analysis of Modified Binders used in Seal Application as a Possible Cause of Observed Highway Distresses (Technical Report No: CSIR/BE/IE/MEMO/2011/0003/B). South Africa: CSIR) also prepared two crumb rubber modified bituminous binders or blends (referred to as CRM Bitumen 1 and CRM Bitumen 2 in Figure 2-5) using the same crumb rubber and blending method as O'Connell et al. but with different base bituminous binders from two separate refineries. It was noted that "the viscosity of the CRM blends conformed to the recommended viscosity range after 6-7 hours of mixing at 190-200°C (i.e. 6-7 hours from the point referred to as 0 hour), see Figure 2-5. The blends stayed in this viscosity range for a limited time frame before falling below the minimum required viscosity limit of 2000 mPa.s.
Although the two blends displayed similar digestion curves, they still showed different field performance when used for surfacing seals. The one binder (CRM Bitumen 2 of
Figure 2-5) was a lot softer in the field resulting in flushing and atypical stone orientation (see Figure 2-6).
Figure 2-7 shows softening points with digestion of the same two binders (CRM Bitumen 1 and CRM Bitumen 2) shown in Figure 2-5. Upon blending, the blend used in the nonflushing area (CRM Bitumen 1) had a much higher softening point than the required TG 1 (2007) maximum limit. In contrast, the softening point of the blend from the flushing area (CRM Bitumen 2) (following blending) conformed to the set maximum criterion. After 6-7 hours of digestion, the softening point of the flushing area blend fell below the minimum specification limit. This is precisely the time the blend conformed to the required application viscosity range in Figure 2-5. So if a contractor waited for the blend viscosity to reach the recommended range, this would explain the softer binder experienced in the field that could have contributed to the observed distress. Mturi et al. however acknowledged that other factors may have also played a role in the observed distress. It is to be noted that the softening point of the non-flushing area blend conformed to the required limits from 6-7 hours of digestion up to 30 hours of digestion.
It can be concluded that the use of digestion viscosity curves to predict performance of crumb rubber modified bituminous binders may be misleading because viscosity is tested at much higher handling temperatures (190-200°C) which may not be simulative of field performance (e.g. in an asphalt pavement) at in-service temperatures (<70°C).
Figure 2-8 illustrates softening points with digestion of crumb rubber modified bituminous blends (CRM blend (CR1) and CRM blend (CR2)), re-blended with additional crumb rubber (CR) once over-digested. For this exercise, two different types of crumb rubber were used while keeping the rest of the material/process parameters constant. The figure shows softening points of the crumb rubber modified bituminous blends approaching that of the base bituminous binder with over-digestion. Once the blends were supplemented with extra crumb rubber, the over-digested binder regained the higher softening point values and retained them with prolonged digestion.
Notably, the minimum softening points of the two over-digested crumb rubber modified bituminous blends and of the two re-blends (with digestion) were relatively similar,
even though the digestion curves for the two crumb rubber types appeared slightly different. It can be considered that the softening points of the base bituminous binder and the over-digested bituminous binder (considered the base binder of the re-blend) act as limits preventing any further drop in softening points with continued digestion. This proves that the properties of the base binder are just as important in the manufacture of crumb rubber modified bituminous binders and can also be specified according to climatic conditions.
Crumb rubber modified bituminous binder residues taken at various digestion time intervals were analysed for their stress sensitivity (i.e. sensitivity to traffic loading). The test method employed is referred to as the multiple stress creep and recovery (MSCR) test. The MSCR test as per ASTM D7405 or AASHTO T350 evaluates the ability of binders to maintain elastic response at the stress levels of 100 Pa and 3200 Pa using a dynamic shear rheometer (DSR). The test involves applying a 1-second creep loading followed by a 9-second recovery phase, and this constitutes a single cycle. At each stress level, 10 creep and recovery cycles are applied. The modified test procedure adopted for this investigation uses multiple stress levels of 25, 50, 100, 200, 400, 800, 1600, 3200, 6400, 12800 and 25600 Pa. The average non-recovered strain (ynr) for the 10 creep and recovery cycles is then divided by the applied stress (T) for those cycles yielding the non-recoverable creep compliance (Jnr = Ynr/x). The accumulation of Jnr over time will eventually lead to permanent deformation.
The MSCR test was modified to adopt multiple stress loading conditions because an in situ binder in an asphalt layer experiences a wide range of stresses from the passing of light to heavy vehicles. It is the higher stresses experienced under repetitive heavy vehicle loads that would eventually be responsible for pavement deformation. Therefore, it is at higher stress loading conditions that binders are better evaluated in terms of their damage resistance properties.
Figure 2-9 shows the MSCR test results of the crumb rubber modified bituminous binders or blends. The test results graphically illustrated in Figure 2-9 show that the drop in crumb rubber modified bituminous binder or blend stiffness expected with digestion time is accompanied by an increase in stress sensitivity. Re-stiffening the over-digested crumb rubber
modified bituminous binder with a modifier or additive should therefore be assessed as to whether it also improves stress resilience.
It is important to note that the behaviour observed in Figures 2-8 and 2-9 applies to the particular crumb rubber modified bituminous blends tested. This behaviour would need to be repeated and confirmed with other crumb rubber modified bituminous blends accordingly.
The foregoing investigations have shown that in order to make an over-digested crumb rubber modified bituminous binder useful again, re-stiffening the over-digested crumb rubber modified bituminous binder should specifically improve:
(1) In-service properties (such as softening point instead of viscosity at 190°C),
(2) Stress resilience, and
(3) Stability.
An ideal additive should recreate a network to recombine lower molecular weight oily constituents and consequently improve stiffness and storage stability properties of an overdigested crumb rubber modified bituminous binder. An investigation with a range of additives came up with the following findings:
• Temporary network forming non-reactive additives (e.g. fillers, styrene-butadiene- styrene, etc.) were found unsuitable because they increased the stress sensitivity of overdigested crumb rubber modified bituminous binders.
• Reactive additives improved the stress resilience properties of over-digested crumb rubber modified bituminous binders.
• Elasticity-inducing additives (e.g. terpolymers containing butyl acrylate at 28 wt% and glycidyl methacrylate at 5.3 wt%) had very little effect on stiffness properties of overdigested crumb rubber modified bituminous binder.
• Stiffness-inducing additives (e.g. ethylene-vinyl acetate) had the highest effect on the stiffness of over-digested crumb rubber modified bituminous binders. Ethylene-vinyl acetate is however non-reactive in bituminous blends.
Based on the investigations which the inventor was involved with, and the conclusions reached, the inventor decided that reactive elastomeric terpolymers (referred to as
SI(RET) below), e.g. a terpolymer of ethylene, alkyl acrylate and glycidyl methacrylate (GMA) would be ideally suited for re-stiffening an over-digested crumb rubber modified bituminous binder. The inventor believes that the GMA group would react with available functional groups as it reacts (supposedly) with carboxylic functional groups in bituminous asphaltenes fractions:
Force ductility curves of modified penetration grade bitumens however showed that only specific terpolymer formulations were highly reactive and hence sufficiently stiffnessinducing (as opposed to elasticity-inducing) for purposes of re-stiffening an over-digested crumb rubber modified bituminous binder sufficiently (see Figure 3-1).
The addition of stiffness-inducing reactive elastomeric terpolymer to form polymer linkages with the over-digested crumb rubber modified bituminous binder (over digested CRM binder) was monitored through average molar mass and molar mass distribution determination, as shown in Figure 3-2. In this particular case, the stiffness-inducing reactive elastomeric terpolymer additive (SI RET) used was an ethylene/n-butyl acrylate/glycidyl methacrylate terpolymer (at 9% GMA). Figure 3-2 also shows the molar mass distribution of pure 70/100 penetration grade bitumen (Pure 10/100pen).
The crumb rubber modified bituminous binder was prepared at temperatures between 190-200°C on a hot plate with a 4 bladed stainless-steel propeller (paddle stirrer) at a speed of 1500-2000rpm. The crumb rubber modified bituminous binder was maintained at this
temperature until complete over digestion, notably where stable/consistent properties were achieved after 32-33 hours of stirring. 1% (m/m) SI RET additive was added to the over-digested blend without changing the stirring speed. The sample was stirred for a further 2 hours continuously. All blends were checked periodically and adjustments to the stirrer position done as the viscosity changed.
There was no addition of poly-phosphoric acid (PPA). When added alone or in combination with the SI RET additive, PPA was found negatively to affect the properties of the bituminous binder.
The SI RET additive increased the softening point (SP) of the over-digested binder (CRM blend (CR 1)) to a level similar to the original crumb rubber (CR) modified bituminous blend or binder. It also improved the storage stability of the re-stiffened blend as shown in Figure 3-3. The stiffness-inducing reactive elastomeric terpolymer additive and crumb rubber modified bituminous blend (over digested binder + SI RET) also exhibited improved stress resilience as shown in Figure 3-4 which shows graphs for the original crumb rubber modified bituminous binder (CRM binder (original)), the over-digested crumb rubber modified bituminous binder (over digested binder) and the stiffness-inducing reactive elastomeric terpolymer additive and crumb rubber modified bituminous blend (Over digested binder + SI RET), and increased stiffness and reduced elastic properties at high in-service temperatures (see Figure 3-5), when compared with over-digested crumb rubber modified bituminous binder (over digested binder). Based on TGI (2015) guideline recommendations, the stiffness-inducing reactive elastomeric terpolymer additive and crumb rubber modified bituminous blend was found conforming to both A-Rl (for asphalt) and S-Rl (for seals) classes for all tested properties except viscosity at 190°C (as expected given it was over-digested), as shown in Table 3-1.
Table 3-1: TGI (2015) properties of over-digested crumb rubber modified bituminous binder restiffened with a stiffness-inducing reactive elastomeric terpolymer (SI RET) additive.
Class
Test
PROPERTY Unit Results (TGI, 2015)
Method _
S-Rl A-Rl
Softening Point °C 61.0 - 61.4 MB-17 55-65 55-65
Dynamic Viscosity dPa.s 8.0 MB-13 20-40 20-50 at 190°C
Compression
Recovery
After 5 mins 85.6 MB-11 >70 >80
1 hour 85.6 >70 >70
24 %
69.9 >40 N/A hours
4 days 67.9 N/A N/A
Resilience at 25°C % 17.3 MB-10 13-35 13-40
Flow mm 28 MB-12 15-70 10-50
The stiffness-inducing reactive elastomeric terpolymer additive and crumb rubber modified bituminous blend or binder (re-stiffened binder) was investigated against a crumb rubber modified bituminous binder and a styrene-butadiene-styrene (SBS) modified bituminous binder in terms of permanent deformation resistance in asphalt mixes. Asphalt mixes were prepared using typical optimized mix designs used for road construction in South Africa, namely a bitumen rubber asphalt semi-open graded mix (BRASO) and a medium continuously graded mix (A-E2 SBS).
The mixing and compaction of specimens were done in accordance with CSIR test protocols. The mixes were prepared using a heated mechanical mixer into which the calculated masses of aggregate and bituminous binder were placed. Aggregates were blended in accordance with the design grading. The materials were mixed for approximately 5 minutes or
until a uniform mixture was obtained. After mixing, the material was placed in an oven set at compaction temperature for four hours to induce short-term ageing, after which the mix was compacted. Gyratory specimens for performance testing were compacted to a density of between 92 and 94 percent of the Maximum Theoretical Relative Density (MTRD). The resultant cored gyratory specimens were used to perform a repeated load permanent deformation (RLPD) test.
The medium continuously graded mixes were prepared at the CSIR advanced road material testing laboratories using a standard SBS binder and an over-digested crumb rubber modified bituminous binder comprising SI RET additive (i.e. re-stiffened binder). Air voids and binder contents in the laboratory testing programme simulated the properties of the field mixes as best as possible. The original design was done using the Marshall Mix design method as per COLTO (1998) with the Interim Guidelines for the Design of Hot Mix Asphalt (2001). Table 4-1 shows the target binder and air voids contents as well as other volumetric properties of the mix.
After compaction, the densities (MTRD and BRD) were determined using the standard TMH1 C3 method. The results for the specimens tested are shown in Tables 4-2 and 4- 3 for the SBS mix (specimen 14383) and the re-stiffened binder (specimen 14706). The voids content for the performance tests specimens were within 6% to 8% voids content.
Table 4-1: Summary of volumetric properties of the medium continuous mix
Table 4-2: Gyratory specimens' densities (before and after coring) for the SBS mix
*Original mix results produced in the development of the SABITA Asphalt Mix Design Manual for South Africa (2014) (SABITA Draft Manual, Asphalt mix design manual for South Africa - provisional working document, SABITA, Howard Place, South Africa, 2014).
Based on AASHTO TP 79 (2009) and NCHRP Report 702 (2011), the rutting resistance behaviour of the mixes was investigated. The UTM-25 test setup for dynamic modulus testing was used to conduct the test. Gyratory compacted specimens size of 100 mm diameter and 150mm high cored from cylindrical medium continuous specimens of 150 mm in diameter by 170 mm high were tested.
The permanent deformation experimental design consisted of a single applied stress (deviator stress) level of 600 kPa at 40°C. The deviator stress was repeatedly pulsed in the vertical direction on the specimens using a haversine pulse load of 0.1 seconds and 0.9 seconds rest period until flow or 10,000 load cycles.
Table 4-4 shows a summary of the test results that includes specimen air voids content, test temperatures, and the loading conditions. Specimens were tested at close to field voids. Figure 4-1 shows the average permanent strain accumulations in the test samples against the number of load applications at the applied deviator stress level of 600 kPa and test temperature of 40°C.
The re-stiffened over-digested crumb rubber modified bituminous mix (MOD-CR
Mix) showed better permanent deformation resistance than the SBS mixes (both the original SBS Mix used with this mix design and the repeated SBS Mix manufactured for this exercise) at the tested temperature.
*Original mix results produced in the development of the SABITA Asphalt Mix Design Manual for South Africa (2014).
The BRASO mixes were prepared at the CSIR advanced road material testing laboratories using a standard crumb rubber modified bituminous binder and an over-digested crumb rubber modified bituminous binder comprising SI RET additive (i.e. re-stiffened binder). Air voids and binder contents in the laboratory-testing programme simulated the properties of the field mixes as best as possible. The original design was done using the Marshall mix design method as per SABITA Manual 19, 2007 with the Interim Guidelines for the Design of Hot Mix Asphalt (2001). Table 4-5 shows the target binder and air voids contents as well as other design properties of the mix.
After compaction, the densities (MTRD and BRD) were determined using the standard TMH1 C3 method. The results for the specimens tested are shown in Tables 4-6 and 4- 7 for the crumb rubber modified bituminous mix (specimen 14536) and the re-stiffened mix respectively (specimen 14697). The voids content for the performance tests specimens were within 6% to 8% voids content.
Table 4-6: Gyratory specimens densities (before and after coring) for the crumb rubber modified mix
* Lab sample (prepared at the CSIR)
** Plant sample
Based on AASHTO TP 79 (2009) and NCHRP Report 702 (2011), the rutting resistance behaviour of the mixes was investigated. The UTM-25 test setup for dynamic modulus testing was used to conduct the test. Gyratory compacted specimens size of 100 mm diameter and 150mm high cored from cylindrical medium continuous specimens of 150 mm in diameter by 170 mm high were tested.
The permanent deformation experimental design consisted of a single applied stress (deviator stress) level of 276 kPa and 69kPa confinement pressure at 40°C. The deviator stress was repeatedly pulsed in the vertical direction on the specimens using a haversine pulse load of 0.1 seconds and 0.9 seconds rest period until flow or 10,000 load cycles.
Table 4-8 shows a summary of the test results that include specimen air voids content, test temperatures, and the loading conditions. Specimens were tested at close to field voids. Figure 4-2 shows the average permanent strain accumulations in the test samples against the number of load applications at the applied deviator stress level of 276 kPa with a confining pressure of 69kPa and test temperature of 40°C.
The re-stiffened over-digested crumb rubber modified bituminous mix showed better permanent deformation resistance than the standard crumb rubber modified bituminous mix at the tested temperature.
The invention, as illustrated, provides a method to re-stiffen over-digested rubber modified bituminous binders or blends. Over-digested rubber modified bituminous blends restiffened with a stiffness-inducing reactive elastomeric terpolymer additive advantageously produced stiffer, stable and stress resilient homogeneous modified blends.
Larger volumes of re-stiffened bituminous binders were successfully manufactured and incorporated into Hot Mix Asphalt (HMA) designs. The resulting re-stiffened asphalt binder mixes, when compared with standard binders (namely crumb rubber modified bituminous binders and SBS modified bituminous binders) in identical asphalt mix designs containing the same aggregate, grading and binder content, showed superior performance against the standard mixes in terms of rutting resistance from a performance-related laboratory test.
Claims
1. A method of re-stiffening an over-digested rubber modified bituminous binder, the method including admixing a reactive, stiffness inducing organic additive with the over-digested rubber modified bituminous binder to produce a re-stiffened rubber modified bituminous binder with an increased softening point, wherein the admixing takes place at an elevated temperature of at least 185°C.
2. The method according to claim 1, in which the over-digested rubber modified bituminous binder is a rubber modified bituminous binder with a viscosity at 190°C of less than 2000 mPa.s and/or with a softening point of less than 55°C.
3. The method according to claim 1 or claim 2, in which the over-digested rubber modified bituminous binder is completely over-digested so that the over-digested rubber modified bituminous binder has a viscosity approaching that of a base bituminous binder of the rubber modified bituminous binder, once the viscosity has dropped below 2000 mPa.s, and/or so that the over-digested rubber modified bituminous binder has a softening point approaching that of the base binder, once the softening point has dropped below 55°C.
4. The method according to claim 3, which includes digesting the over-digested rubber modified bituminous binder for a period of time sufficient to ensure that the overdigested rubber modified bituminous binder is completely over-digested, prior to admixing the reactive, stiffness inducing organic additive with the over-digested rubber modified bituminous binder.
5. The method according to any of claims 1 to 4, in which the reactive, stiffness inducing organic additive is reactive in the sense that reactions between one or more components of the reactive, stiffness inducing organic additive with functional groups present in the over-digested rubber modified bituminous binder take place, to produce a re-stiffened
rubber modified bituminous binder with an altered composition and an increased softening point.
6. The method according to any of claims 1 to 4, in which the reactive, stiffness inducing organic additive is reactive in the sense that reactions between one or more components of the reactive, stiffness inducing organic additive with functional groups present in the over-digested rubber modified bituminous binder take place to produce a re-stiffened rubber modified bituminous binder with an improved Jnr, and/or an improved storage stability and/or an improved stress resilience.
7. The method according to any of claims 1 to 6, in which the reactive, stiffness inducing organic additive is a reactive elastomeric organic additive.
8. The method according to claim 7, in which the reactive, stiffness inducing organic additive is a reactive elastomeric polymer composition.
9. The method according to claim 8, in which the reactive, stiffness inducing organic additive is a reactive elastomeric terpolymer composition.
10. The method according to claim 9, in which the reactive elastomeric terpolymer composition is a terpolymer of ethylene, an alkyl acrylate and glycidyl methacrylate.
11. The method according to any of claims 1 to 10, in which the admixing takes place at an elevated temperature of between 185°C and 210°C, or between 190°C and 200°C, or between 190°C and 195°C, and/or in which the admixing is for less than 160 minutes, or for less than 145 minutes, or for less than 130 minutes, and at least for 100 minutes, or at least for 110 minutes, or at least for 120 minutes.
12. The method according to any of claims 1 to 11, in which the stiffness inducing organic additive and the over-digested rubber modified binder are admixed in a mass ratio of
between 0.5:99.5 and 2.0:98.0, or between 0.5:99.5 and 1.5:98.5, or between 0.8:99.2 and 1.2:98.8.
13. A re-stiffened rubber modified bituminous binder when produced by the method of re-stiffening an over-digested rubber modified bituminous binder as claimed in any of claims 1 to 12.
14. The re-stiffened rubber modified bituminous binder according to claim 13, which has an increased softening point to at least 56°C, or to at least 58°C, or to at least 60°C, or to at least 61°C.
15. The re-stiffened rubber modified bituminous binder according to claim 13 or claim 14, which shows a reduction in elasticity with an increase in the complex modulus (G*), as evidenced by reduced phase angles at in-service temperatures.
16. A rubber modified bituminous binder, the binder including a digested rubber bituminous admixture with a softening point of at least 55°C and a dynamic viscosity at 190°C of less than 2000 mPa.s.
17. The rubber modified bituminous binder according to claim 16, which has a softening point of at least 56°C, or at least 58°C, or at least 60°C, or at least 61°C.
18. The rubber modified bituminous binder according to claim 16 or claim 17, which has a dynamic viscosity at 190°C of less than 1500 mPa.s, or less than 1200 mPa.s, or less than 1000 mPa.s, or less than 900 mPa.s.
19. The rubber modified bituminous binder according to any of claims 13 to 18, which has a compression recovery at 5 minutes, according to the MB-ll test method as set out in TG 1, 2015, of more than 70%, or more than 80%, or which has a compression recovery after 1 hour, according to the MB-ll test method, of more than 70%, or more than 75%, or more than 80%, or which has a compression recovery after 24 hours, according to the MB-ll test method, of more than 40%, or more than 50%, or more than 60%, or which has a compression recovery after
4 days, according to the MB-ll test method, of more than 40%, or more than 50%, or more than 60%.
20. The rubber modified bituminous binder according any of claims 13 to 19, which has a resilience at 25°C, according to the MB-10 test method as set out in TG 1, 2015, of more than 13%, or more than 14%, or more than 15%.
21. The rubber modified bituminous binder according to any of claims 13 to 20, which flows, according to the MB-12 test method as set out in TG 1, 2015, more than 10mm, or more than 15mm, or more than 20mm, or more than 25mm.
22. The rubber modified bituminous binder according any of claims 13 to 21, which has a weight fraction of at least 0.13, or at least 0.15, or at least 0.18, or at least 0.2 of components with an average molar mass between 3.9xl06 g/mol and 4.1xl06 g/mol.
23. The rubber modified bituminous binder according any of claims 13 to 22, which has a weight fraction of at least 0.13, or at least 0.15, or at least 0.18, or at least 0.2 of components with an average molar mass between 4.1xl06 g/mol and 4.2xl06 g/mol.
24. The rubber modified bituminous binder according any of claims 13 to 23, which includes reaction products from reactions between glycidyl methacrylate and functional groups of the over-digested bituminous binder.
25. A method of sealing or asphalt paving a surface, the method including applying a layer which includes a rubber modified bituminous binder to the surface, the rubber modified bituminous binder being in the form of a digested rubber bitumen admixture with a softening point of at least 55°C and a dynamic viscosity at 190°C of less than 2000 mPa.s.
26. The method of sealing or asphalt paving a surface according to claim 25, in which the layer includes aggregate particles, with the rubber modified bituminous binder and the aggregate particles forming a seal surfacing layer or a layer of an asphalt mix.
37
27. The method of paving a surface according to claim 26, in which the asphalt mix is a medium continuously graded mix and has a maximum displacement, using a Universal Testing Machine test setup, i.e. a UTM-25 test setup for dynamic modulus testing, with gyratory compacted specimens size of 100 mm diameter and 150mm high cored from cylindrical medium continuous specimens of 150 mm in diameter by 170 mm high, a single applied stress or deviator stress level of 276 kPa and 69kPa confinement pressure at 40°C, with the deviator stress repeatedly pulsed in the vertical direction on the specimens using a haversine pulse load of 0.1 seconds and 0.9 seconds rest period until flow or 10,000 load cycles, equal to an identical asphalt SBS mix in terms of mix design, grading, aggregate type and binder content, based on an A-E2 conforming SBS binder, or at least 25% better, or at least 50% better, or more than double, the performance of the identical asphalt SBS mix.
28. The method of paving a surface according to claim 26 or claim 27 , in which the asphalt mix is a medium continuously graded mix and has a flow number, using a UTM-25 test setup for dynamic modulus testing, with gyratory compacted specimens size of 100 mm diameter and 150mm high cored from cylindrical medium continuous specimens of 150 mm in diameter by 170 mm high, a single applied stress or deviator stress level of 276 kPa and 69kPa confinement pressure at 40°C, with the deviator stress repeatedly pulsed in the vertical direction on the specimens using a haversine pulse load of 0.1 seconds and 0.9 seconds rest period until flow or 10,000 load cycles, equal to an identical asphalt SBS mix in terms of mix design, grading, aggregate type and binder content based on an A-E2 conforming SBS binder, or at least 25% better, or at least 50% better, or more than double, the performance of the identical asphalt SBS mix.
29. The method of paving a surface according to claim 26, in which the asphalt mix is a bitumen-rubber asphalt semi-open (BRASO) graded mix and has a maximum displacement, using a UTM-25 test setup for dynamic modulus testing, with gyratory compacted specimens size of 100 mm diameter and 150mm high cored from cylindrical medium continuous specimens of 150 mm in diameter by 170 mm high, a single applied stress or deviator stress level of 276 kPa and 69kPa confinement pressure at 40°C, with the deviator stress repeatedly pulsed in the vertical direction on the specimens using a haversine pulse load of 0.1 seconds and 0.9 seconds rest period until flow or 10,000 load cycles, equal to an identical asphalt mix in terms of mix
design, grading, aggregate type and binder content, based on an A-Rl conforming crumb rubber modified bituminous binder, or at least 25% better, or at least 50% better, or more than double, the performance of the identical asphalt mix based on an A-Rl conforming crumb rubber modified bituminous binder.
30. The method of paving a surface according to claim 26 or claim 29, in which the asphalt mix is a bitumen-rubber asphalt semi-open (BRASO) graded mix and has a flow number, using a UTM-25 test setup for dynamic modulus testing, with gyratory compacted specimens size of 100 mm diameter and 150mm high cored from cylindrical medium continuous specimens of 150 mm in diameter by 170 mm high, a single applied stress or deviator stress level of 276 kPa and 69kPa confinement pressure at 40°C, with the deviator stress repeatedly pulsed in the vertical direction on the specimens using a haversine pulse load of 0.1 seconds and 0.9 seconds rest period until flow or 10,000 load cycles, equal to an identical asphalt mix in terms of mix design, grading, aggregate type and binder content, based on an A-Rl conforming crumb rubber modified bituminous binder, or at least 25% better, or at least 50% better, or more than double, the performance of the identical asphalt mix based on an A-Rl conforming crumb rubber modified bituminous binder.
31. The method of sealing or paving a surface according to any of claims 26 to 30, in which the rubber modified bituminous binder is a binder as claimed in any of claims 13 to 24.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US18/253,635 US20240002625A1 (en) | 2020-11-19 | 2021-11-18 | Rubber modified bituminous binders |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ZA2020/07201 | 2020-11-19 | ||
ZA202007201 | 2020-11-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2022107034A1 true WO2022107034A1 (en) | 2022-05-27 |
Family
ID=78806593
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/IB2021/060691 WO2022107034A1 (en) | 2020-11-19 | 2021-11-18 | Rubber modified bituminous binders |
Country Status (3)
Country | Link |
---|---|
US (1) | US20240002625A1 (en) |
WO (1) | WO2022107034A1 (en) |
ZA (1) | ZA202109237B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115684250A (en) * | 2022-09-01 | 2023-02-03 | 淮安市博彦土木工程科学研究院有限公司 | Method for evaluating heat storage stability of rubber modified asphalt |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5704971A (en) * | 1997-03-04 | 1998-01-06 | Memon; Mohammed | Homogeneous crumb rubber modified asphalt |
WO2010023173A1 (en) * | 2008-08-25 | 2010-03-04 | Shell Internationale Research Maatschappij B.V. | Bitumen composition |
US20150112001A1 (en) * | 2009-03-08 | 2015-04-23 | Rheopave Technologies, Llc | Micronized asphalt modifiers, methods of modifying asphalt, asphalt compositions and methods of making |
US20160024306A1 (en) * | 2014-07-23 | 2016-01-28 | Indian Oil Corporation Limited | Hybrid modified bitumen composition and process of preparation thereof |
-
2021
- 2021-11-18 WO PCT/IB2021/060691 patent/WO2022107034A1/en active Application Filing
- 2021-11-18 ZA ZA2021/09237A patent/ZA202109237B/en unknown
- 2021-11-18 US US18/253,635 patent/US20240002625A1/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5704971A (en) * | 1997-03-04 | 1998-01-06 | Memon; Mohammed | Homogeneous crumb rubber modified asphalt |
WO2010023173A1 (en) * | 2008-08-25 | 2010-03-04 | Shell Internationale Research Maatschappij B.V. | Bitumen composition |
US20150112001A1 (en) * | 2009-03-08 | 2015-04-23 | Rheopave Technologies, Llc | Micronized asphalt modifiers, methods of modifying asphalt, asphalt compositions and methods of making |
US20160024306A1 (en) * | 2014-07-23 | 2016-01-28 | Indian Oil Corporation Limited | Hybrid modified bitumen composition and process of preparation thereof |
Non-Patent Citations (9)
Title |
---|
BULATOVIC VESNA OCELIC ET AL: "Effect of polymer modifiers on the properties of bitumen", JOURNAL OF ELASTOMERS AND PLASTICS, vol. 46, no. 5, 1 August 2014 (2014-08-01), GB, pages 448 - 469, XP055883609, ISSN: 0095-2443, Retrieved from the Internet <URL:http://journals.sagepub.com/doi/full-xml/10.1177/0095244312469964> DOI: 10.1177/0095244312469964 * |
MTURI G.A.J.O'CONNELL J.ZOOROB S.DE BEER M.: "A study of crumb rubber modified bitumen used in South Africa", ROAD MATERIALS AND PAVEMENT DESIGN, vol. 15, 2014, pages 774 - 790 |
MTURI GAJO'CONNELL JMARAIS HHAWES N, A BRIEF ANALYSIS OF OVER-DIGESTED CRUMB RUBBER MODIFIED BITUMEN, RUBBERIZED ASPHALT: ASPHALT RUBBER CONFERENCE, 2015, pages 409 - 419 |
MTURI, G.A.J.O'CONNELL, J.ANOCHIE-BOATENG, J.K.: "Limitations of current South African test methods for bituminous binders", CONSTRUCTION AND BUILDING MATERIALS, vol. 45, 2013, pages 314 - 323, XP028551208, DOI: 10.1016/j.conbuildmat.2013.04.009 |
MTURI, G.CONRAD, S.MOGONEDI, K.: "JR 5023: Analysis of Modified Binders used in Seal Application as a Possible Cause of Observed Highway Distresses", TECHNICAL REPORT NO: CSIR/BE/IE/MEMO/2011/0003/B, 2011 |
MTURI, G.ZOOROB, S.E.O'CONNELL, J.ANOCHIE-BOATENG, J.MAINA, J.: "Rheological testing of crumb rubber modified bitumen", PROCEEDINGS OF THE 7TH INTERNATIONAL COMMITTEE ON ROAD & AIRFIELD PAVEMENT TECHNOLOGY, 2011, pages 1316 - 1327 |
MULLER J.MARAIS H.: "The Perceived versus actual shelf-life and performance properties of bitumen rubber", PROCEEDINGS OF THE ASPHALT RUBBER CONFERENCE, 23 October 2012 (2012-10-23), pages 429 - 441 |
O'CONNELL J.ANOCHIE-BOATENG J.MARAIS H.: "Evaluation of bitumen-rubber asphalt manufactured from modified binder at lower viscosity", PROCEEDINGS OF THE 29TH SOUTHERN AFRICAN TRANSPORT CONFERENCE, 16 August 2010 (2010-08-16), pages 129 - 138 |
TECHNICAL GUIDELINE: "SABITA", 2015, HOWARD PLACE, article "The Use of Modified Bituminous Binders in Road Construction" |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115684250A (en) * | 2022-09-01 | 2023-02-03 | 淮安市博彦土木工程科学研究院有限公司 | Method for evaluating heat storage stability of rubber modified asphalt |
CN115684250B (en) * | 2022-09-01 | 2023-10-24 | 淮安市博彦土木工程科学研究院有限公司 | Evaluation method for thermal storage stability of rubber modified asphalt |
Also Published As
Publication number | Publication date |
---|---|
ZA202109237B (en) | 2023-05-31 |
US20240002625A1 (en) | 2024-01-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Poovaneshvaran et al. | Impacts of recycled crumb rubber powder and natural rubber latex on the modified asphalt rheological behaviour, bonding, and resistance to shear | |
Attaelmanan et al. | Laboratory evaluation of HMA with high density polyethylene as a modifier | |
Chen et al. | Evaluation and optimization of the engineering properties of polymer-modified asphalt | |
Sengoz et al. | Evaluation of the properties and microstructure of SBS and EVA polymer modified bitumen | |
Sengoz et al. | Analysis of styrene-butadiene-styrene polymer modified bitumen using fluorescent microscopy and conventional test methods | |
US20210189133A1 (en) | Recycled oil and rubber-modified asphalt and method of use | |
CN102770494A (en) | Polymer-modified asphalt with a crosslinking agent and methods of preparing | |
Agudelo et al. | Ground tire rubber and bitumen with wax and its application in a real highway | |
You et al. | Use of amorphous-poly-alpha-olefin as an additive to improve terminal blend rubberized asphalt | |
Thives et al. | Assessment of the digestion time of asphalt rubber binder based on microscopy analysis | |
Ameli et al. | The effects of gilsonite and crumb rubber on moisture damage resistance of stone matrix asphalt mixtures | |
Naveed et al. | Effect of mineral fillers on the performance, rheological and dynamic viscosity measurements of asphalt mastic | |
Azahar et al. | Engineering properties of asphalt binder modified with cup lump rubber | |
Xu et al. | Effects of the high temperature and heavy load on the rutting resistance of cold-mix emulsified asphalt mixture | |
US20240002625A1 (en) | Rubber modified bituminous binders | |
Bairgi et al. | Investigation of rheological properties of asphalt rubber toward sustainable use of scrap tires | |
Ezzat et al. | The influence of using hybrid polymers, aggregate gradation and fillers on moisture sensitivity of asphaltic mixtures | |
Romastarika et al. | Effect of black rice husk ash on the physical and rheological properties of bitumen | |
Aboud et al. | Effect of polymer’s type and content on tensile strength of polymers modified asphalt mixes | |
US10240040B2 (en) | Method of making sulfur extended asphalt modified with crumb rubber | |
Mohamed et al. | Rheological properties of crumb rubber modified bitumen containing antioxidant | |
Muniandy et al. | Influence of mineral filler particle size and type on rheological and performance properties of SMA asphalt-filler mastics | |
Erkuş et al. | The effects of Iraq natural asphalt on mechanical properties of bituminous hot mixtures | |
Samal et al. | The polymer effects on bitumen performance properties in Kazakhstan | |
Tarsi et al. | Rheo-mechanical analysis of bitumens produced with green binder extenders |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21815690 Country of ref document: EP Kind code of ref document: A1 |
|
DPE1 | Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101) | ||
WWE | Wipo information: entry into national phase |
Ref document number: 18253635 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 21815690 Country of ref document: EP Kind code of ref document: A1 |